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US009770709B2 (12 ) United States Patent ( 10) Patent No. : US 9 ,770 , 709 B2 Swager et al. (45 ) Date of Patent: * Sep . 26 , 2017 (54 ) COMPOSITIONS COMPRISING C07C 235 /40 (2013 . 01 ) ; CO7D 303 /38 FUNCTIONALIZED CARBON - BASED (2013 . 01 ) ; CO7D 493/ 22 (2013 . 01 ) ; CO7F 1/ 08 NANOSTRUCTURES AND RELATED ( 2013 .01 ); C07F 5 / 00 ( 2013 .01 ); C07F 5 / 06 METHODS (2013 . 01 ) ; C07F 7/ 28 (2013 .01 ); C07F 15 /006 (2013 .01 ) ; CO7F 15 /02 ( 2013. 01 ) ; HONG (71 ) Applicant: Massachusetts Institute of 11 /36 (2013 . 01 ) ; HOTM 4 /625 ( 2013 .01 ); YO2E Technology , Cambridge, MA (US ) 60 / 13 ( 2013 .01 ) (58 ) Field of Classification Search (72 ) Inventors : Timothy M . Swager, Newton , MA CPC ...... CO1B 31 /0213 ; C01B 31 /0484 ; C01B (US ) ; William R . Collins, Durango , 31/ 0273 ; B82Y 40 / 00 ; B82Y 30 / 00 ; CO (US ) ; Wiktor Lewandowski, A24D 3 / 163 ; C07D 493 / 22 ; C07D Warsaw (PL ) ; Ezequiel Schmois , 303 /38 ; H016 11 / 36 ; CO7F 5 /06 ; CO7F Cambridge , MA (US ); Stefanie Sydlik , 5 / 00 ; C07F 7 /28 ; CO7F 1 / 08 ; C07F Cambridge, MA (US ); Joseph Walish , 15 / 006 ; CO7F 15/ 02 ; B01J 31/ 12 ; C07C Cambridge , MA ( US ) ; John B . Goods , 235 / 40 ; HOTM 4 /625 ; YO2E 60 / 13 Cambridge, MA (US ) USPC ...... 534 / 15 ; 549 /543 ; 556 / 112 , 136 , 140 , ( 73 ) Assignee: Massachusetts Institute of 556 / 170 , 52 ; 562/ 507 Technology , Cambridge , MA (US ) See application file for complete search history. ( * ) Notice : Subject to any disclaimer , the term of this (56 ) References Cited patent is extended or adjusted under 35 U .S . C . 154 (b ) by 5 days. U . S . PATENT DOCUMENTS 3 ,450 , 878 A 6 / 1969 Pezdirtz et al. This patent is subject to a terminal dis 3 , 915 ,706 A 10 / 1975 Limburg et al. claimer. 4 ,616 ,237 A 10 / 1986 Pettigrew et al . 5 , 753 ,088 A 5 / 1998 Olk (21 ) Appl. No. : 14 /670 , 232 6 ,616 , 497 B1 9 / 2003 Choi et al. 6 , 652 , 958 B2 11/ 2003 Tobita 6 , 705 , 910 B2 3 /2004 Sheu et al. ( 22 ) Filed : Mar . 26 , 2015 6 , 902 , 658 B2 6 / 2005 Talin et al. 6 , 958 , 216 B2 10 / 2005 Kelley et al . (65 ) Prior Publication Data 7 , 014 , 743 B2 3 / 2006 Zhou et al. 7 , 187 , 115 B2 3 /2007 Seon US 2015/ 0336092 A1 Nov. 26 , 2015 7 ,303 , 875 B1 . 12 /2007 Bock et al. 7 ,365 , 100 B2 4 / 2008 Kuper et al. Related U . S . Application Data 7 , 556, 775 B2 7/ 2009 McGill et al . 7 , 854 ,826 B2 12 / 2010 So et al. (63 ) Continuation of application No. 13/ 288 , 769, filed on 7 , 871 , 533 B11 / 2011 Haiping et al. Nov . 3 , 2011 , now abandoned . 8 ,187 , 887 B2 5 /2012 Swager et al. ( 60 ) Provisional application No . 61/ 409, 844 , filed on Nov . ( Continued ) 3 , 2010 . FOREIGN PATENT DOCUMENTS (51 ) Int . CI. 1995143 A 7 / 2007 CO7F 7 / 28 ( 2006 .01 ) 63 - 221278 A 9 / 1988 CO7F 15 / 00 ( 2006 .01 ) 2007 -524735 A 8 /2007 CO7F 15 /02 ( 2006 . 01 ) 2008 -047855 A 2 / 2008 CO7F 5 / 06 ( 2006 . 01 ) ZEEEE 2008 -520414 A 6 /2008 CO7F 1 /08 ( 2006 .01 ) ( Continued ) B01J 31/ 12 ( 2006 .01 ) C07C 235 /40 ( 2006 .01 ) OTHER PUBLICATIONS CO7D 303 /38 ( 2006 .01 ) CO7F 5 / 00 ( 2006 . 01 ) Shu et al. , Electrochemical Intercalation of Lithium into Graphite . COIB 31 /02 ( 2006 .01 ) J . Electrochem . Soc . Apr. 1993 ; 140 ( 4 ): 922 - 927 . COIB 31 /04 ( 2006 . 01 ) (Continued ) C07D 493 /22 ( 2006 .01 ) A24D 3/ 16 ( 2006 .01 ) Primary Examiner — Daniel C McCracken HOIG 11/ 36 ( 2013 . 01 ) (74 ) Attorney , Agent, or Firm — Wolf , Greenfield & B82Y 30 /00 ( 2011 .01 ) Sacks, P . C . B82Y 40 / 00 ( 2011 . 01 ) HOIM 4 /62 ( 2006 .01 ) (57 ) ABSTRACT ( 52 ) U . S . CI. The present invention generally relates to compositions CPC ...... B01J 31/ 12 (2013 .01 ); A24D 3 / 163 comprising and methods for forming functionalized carbon (2013 .01 ) ; B82Y 30 /00 ( 2013 .01 ) ; B82Y 40/ 00 based nanostructures . (2013 .01 ) ; COIB 31/ 0213 ( 2013 .01 ); COIB 31/ 0273 ( 2013 . 01 ) ; COIB 31/ 0484 ( 2013 .01 ) ; 18 Claims, 31 Drawing Sheets US 9 , 770 , 709 B2 Page 2

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Atomic wt% Time % 0 % (O ) % (N )

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0 . 1 N ACOH Fig . 130

Sample Zeta Potential Sample Conductivity (mv ) [ S / m ] GO w19 .5 Insulator Carboxylic Acid - 34 , 1 Carboxylic Acid 3 .74 Potassium Salt Carboxylic Acid Carboxylate - 58 . 6 (Annealed 250°C ) 138 . 2 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 0 . 3 RAROROOROORORORORROR WANNNNNNNNNNNNNNNNNNNNN 80 000 . 000 . 000000. .000 .000 Fig . 13D U . S . Patent Sep . 26 , 2017 Sheet 18 of 31 US 9, 770 ,709 B2

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coladen Cigarettesmoke US 9 ,770 ,709 B2 COMPOSITIONS COMPRISING SUMMARY OF THE INVENTION FUNCTIONALIZED CARBON - BASED NANOSTRUCTURES AND RELATED In someaspects of the present invention , compositions are METHODS provided . In some embodiments , a composition comprises 5 graphene or graphene oxide comprising at least one func RELATED APPLICATIONS tional group associated with the graphene or graphene oxide, wherein the at least one functional group has the structure : This application is a continuation of U . S . patent applica tion Ser. No. 13 / 288 , 769, filed Nov . 3 , 2011 , entitled “ Com positions Comprising Functionalized Carbon - Based Nano 23 structures and Related Methods , ” by Swager, et al. , which claims priority under 35 U . S . C . 8119 ( e ) to U . S . Provisional Patent Application No . 61/ 409, 844, filed Nov. 3 , 2010 , and 94 entitled “ Compositions Comprising and Methods for Form 15 ing Functionalized Carbon - Based Nanostructures ” by Swa ger, et al ., each of which is incorporated herein by reference wherein R1, R2, and R3 are the same or different and each is in its entirety for all purposes . independently a substituent, optionally substituted ; and G comprises a carbon atom of the graphene or graphene oxide In other aspects of the present invention , methods are GOVERNMENT SUPPORT provided . In some embodiments , a method for fabricating a functionalized carbon -based nanostructure comprises pro This invention was made with government support under viding a carbon -based nanostructure comprising an allylic Grant No. HM1582 - 09 - 1 - 0025 awarded by the National functional group , reacting the carbon -based nanostructure Geospatial Intelligence Agency. The government has certain with a reactant comprising at least one carbon atom , and rights in this invention . causing a carbon -carbon bond to form between the at least one carbon atom within the reactant and a carbon atom FIELD OF THE INVENTION within the carbon -based nanostructure . In another embodi ment , a method for fabricating a functionalized carbon The present invention generally relates to compositions based nanostructure comprises providing a carbon -based comprising and methods for forming or using functionalized so30 nannanostructure including a group having the formula ( I ) : carbon - based nanostructures . BACKGROUND OF THE INVENTION Carbon -based nanostructures, including two - dimensional 35 ORS, graphene nanosheets and graphene- based materials , have C = C2 — 03 garnered an increasingly large amount of scientific interest in recent years due to their structural and electronic prop erties. Conventional methods for synthesizing graphene wherein C1, C2 , and C3 are part of a fused network of based materials utilize graphite oxide (GO ) as a starting 4010 aromatic rings within the carbon - based nanostructure and material, which can be prepared in bulk quantities from ORS is a pendant group of the fused network of aromatic commercial - grade graphite under strong oxidizing condi rings, wherein R is a substituent, optionally substituted , and tions . GO in its bulk form is a lavered material composed of reacting the carbon -based nanostructure with a reactant to a variety of oxygen -containing functionalities, for example , proproduce a group having formula ( II ): epoxides and tertiary alcohol groups are generally found on 45 the basal plane and carbonyl and carboxyl groups along the sheet edges . The diversity and density of functionality in GO provides a platform for chemistry to occur both within the intersheet gallery and along sheet edges . Despite the recent c = 0 upsurge in methods for forming graphene derivatives along 50 with subsequent incorporation of the products into gra R6 phene -based devices , only a few methods exist to covalently - cl = c2 = 3, functionalize the basal plane of graphene. Moreover , current methodology often introduces basal plane functionalities wherein R®, R7, and R8 are the same or different and each is that are weakly bound to the graphene surface through 55 independently a substituent, optionally substituted . carbon - oxygen ( C — 0 ) or carbon - nitrogen ( C — N ) bonds In some embodiments , a device comprising a composition and therefore , the resulting material generally cannot sur as described herein and / or a composition formed using a vive further thermal, electrochemical, and / or chemical treat- method as described herein are provided . In another aspect, ment of the graphene -based material. The labile nature of the present invention encompasses methods of making one such chemical functionalities represents a significant draw - 60 or more of the embodiments described herein . In still back to the currently available technology , as in many cases another aspect , the present invention encompasses methods it is necessary to deoxygenate the graphene derivatives of using one or more of the embodiments described herein . under relatively harsh conditions to reestablish electrical In some embodiments , a method for reducing the amount conductivity within the graphene nanosheet . Additionally, of an species in a sample is provided . In some cases , the incorporation of these C — 0 or C - N modified graphene 65 method comprises contacting a vapor phase sample contain materials into devices can intrinsically limit the thermal ing a first concentration of the species with a composition and / or electrochemical boundaries of the device . comprising substituted graphene or graphene oxide mol US 9 ,770 , 709 B2 ecules such that the vapor phase sample has a second , FIG . 2A shows XPS data ofmaterials , including materials decreased concentration of the species after contact with the of the present invention , according to some embodiments . composition . FIG . 2B shows XPS data of materials , including materials In some embodiments , the method comprises contacting of the present invention , according to some embodiments. a sample containing a first concentration of the species with 5 FIG . 3A shows hi- res XPS data of materials, including a composition comprising graphene or graphene oxide , Sent some embodiments . wherein the graphene or graphene oxide comprises at least FIG . 3B shows hi- res XPS data of materials , including one functional group having the structure : materials of the present invention , according to some 10 embodiments . pu FIG . 4 shows TGA and dTGA spectra of materials , including materials of the present invention , according to some embodiments . OS FIG . 5 shows XRD spectra of materials , including mate rials of the present invention , according to some embodi ments . FIG . 6 shows FTIR spectra of materials , including mate wherein R1, R² , and R3 are the same or different and each rials of the present invention , according to some embodi is a substituent, optionally substituted ; and ments . FIG . 7 shows solutions of materials of the present G comprises a carbon atom of the graphene or graphene 20 invention , according to some embodiments . oxide, FIG . 8 shows an illustrative example of protonated and such that the sample has a second , decreased concentra - unprotonated forms of functionalized graphene , according to tion of species after contact with the composition . some embodiments . In some embodiments , a catalyst composition is provided . FIG . 9 shows an oxidized graphene sheet functionalized In some cases , the catalyst composition comprises a gra - 25 with amide groups undergoing a redox reaction such that phene or graphene oxide molecule comprising at least one charge from the graphene layer is delocalized onto the amide functional group having the structure : nitrogen . FIG . 10 shows the conversion of carbon -oxygen bonds on a graphite oxide basal plane to carbon -bound carbonyl 30 groups . FIG . 11A shows a synthesis of allylic amide - functional ized graphene; ?? FIG . 11B shows a space - filling model of the synthesis of allylic amide- functionalized graphene ; FIG . 11C shows a photograph of a solution of graphene oxide and an aliquot taken 1 hour after the reaction of wherein : graphene oxide with [ (CH3 )2N ]C (OCH3 ) 2CH3 ; R ' , R? , and Rºare the same or different and each is FIG . 11D shows an FTIR spectrum of allylic amide independently a substituent, optionally substituted , wherein functionalized graphene oxide : at least one of R ' , R ' , and R comprises a catalytic moiety 40 FIG . 11E shows X - ray diffraction plot for graphite , gra capable of oxidizing carbon monoxide to carbon dioxide ; phene oxide , and allylic amide - functionalized graphene and oxide ; G comprises a carbon atom of the graphene or graphene FIG . 11F shows X - ray photoelectron spectroscopy (XPS ) oxide. plots for graphene oxide, and allylic amide - functionalized In some embodiments , the method comprises contacting 45 graphene oxide : and a sample comprising carbon monoxide with a graphene or FIG . 11G shows XPS data for graphene oxide , and allylic graphene oxide molecule comprising at least one functional amide - functionalized graphene oxide . group having the structure : FIG . 12A shows the saponification of an allylic ester functionalized graphene oxide ; 50 FIG . 12B shows XPS data ; and Pus FIG . 12C shows XPS plot for a carboxylic acid - function alized graphene oxide . FIG . 13A shows the reversible conversion of carboxylic acid - functionalized graphene oxide to a potassium salt car 55 boxylate - functionalized graphene oxide; FIG . 13B shows the reversible formation of aqueous wherein : colloids containing potassium salt carboxylate - functional R , R² , and R3 are the same or different and each is ized graphene oxide from carboxylic acid - functionalized independently hydrogen or a substituent , optionally substi - graphene oxide ; tuted ; and 60 FIG . 13C shows a photograph of solutions of carboxylic G comprises a carbon atom of the graphene or graphene acid - functionalized graphene oxide under various condi oxide . tions ; FIG . 13D shows zeta potential and conductivity data for BRIEF DESCRIPTION OF THE DRAWINGS carboxylic acid - functionalized graphene oxides . 65 FIG . 14A shows the synthesis of allyl allylic ester FIG . 1 shows non - limiting images of a reaction of the functionalized graphene oxide via a Johnson -Claisen rear present invention , according to some embodiments . rangement ; US 9 ,770 ,709 B2 FIG . 14B shows saponification of an allyl allylic ester generally refers to an oxygenated form of the common functionalized graphene oxide ; carbon allotrope graphene, and is readily available and FIG . 14C shows transamidation of an allyl allylic ester generally inexpensive . The methods described herein not functionalized graphene oxide ; only allow for chemically functionalizing the graphene FIG . 14D shows synthesis of graphene oxides with func- 5 oxide , but also may allow for subsequent deoxygenation of tional group containing an alkyne for “ click ” chemistry the graphene oxide following functionalization , e . g . , without reactions ; causing disassociation or decomposition of the chemical FIG . 14E shows an FTIR spectrum of graphene oxide functionalities. For example , a two -step procedure can be substituted with CH , ( C = O )NHCH , C = CCH ; utilized according to certain embodiments , comprising 1 ) FIG . 14F shows FTIR spectra for various substituted 10 oxidation with concomitant exfoliation to graphene oxide , graphene oxides ; and FIG . 14G shows XRD plots for and 2 ) chemical, electrochemical, or thermal reduction to various substituted graphene oxides. reestablish molecular conjugation and conductivity of the FIG . 15A shows the synthesis of functionalized graphene graphene oxide . oxides via a Carroll rearrangement; In some cases , the method comprises functionalizing FIG . 15B shows illustrative reaction conditions for syn - 15 graphene oxide with a plurality of functional groups , thesizing functionalized graphene oxides via a Carroll rear - wherein each functional group is associated with ( e . g . , rangement; attached to ) the graphene network via a carbon -carbon bond . FIG . 15C shows formation of an acyl ketene according to The carbon -carbon bond formed during functionalization one embodiment; may be capable of withstanding conditions necessary for FIG . 15D shows formation of an acyl ketene according to 20 further functionalizing the graphene and /or the functional another embodiment; and groups, and / or reduction of the graphene. In some cases, the FIG . 15E shows illustrative embodiments for synthesis of methods utilize relatively non -toxic and / or essentially non functionalized graphene oxides . toxic materials as compared to currently known methods. FIG . 16 shows thermogravimetric analysis data for vari In some embodiments , the compositions and methods ous functionalized graphenes compared to unsubstituted 25 described herein provide carbon -based nanostructures , such graphene and unsubstituted graphene with physioadsorbed as graphene oxide or graphene , comprising functional groups . groups associated with the carbon -based nanostructure , gen FIG . 17 shows X - ray diffraction data for graphene cova erally via a carbon - carbon bond , wherein the functional lently functionalized on the basal plane . group comprise a carbonyl group ( e . g . , ester, carboxylic FIG . 18 shows XPS data for graphene covalently func - 30 acid , carboxylate , aldehyde , amide , ketone , any of which is tionalized on the basal plane . optionally substituted ) . In some cases, the carbonyl group is FIG . 19 shows a photograph of various samples contain - an allylic carbonyl group. The carbonyl groups may be ing covalently functionalized graphene , graphene with phys - further functionalized and may provide access to materials ioadsorbed groups, and unsubstituted graphene . useful in a variety of applications. For example , the carbonyl FIG . 20 shows the use of a composition described herein 35 groups may bind metal ions, and may find use as molecular as a filter for cigarette smoke . scaffolds for metal nanoparticles ( e . g ., for catalytic pro Other aspects , embodiments , and features of the invention cesses , for chemosensing ) or to trap metal ions. In some will become apparent from the following detailed descrip - cases , the compositions can be used as an n - type material tion when considered in conjunction with the accompanying ( e . g ., electron transport semiconductor) for various applica drawings. The accompanying figures are schematic and are 40 tions including quantum -dot based photovoltaic cells . In not intended to be drawn to scale . For purposes of clarity , not other cases, the compositions may be used as an anode every component is labeled in every figure , nor is every and / or cathode material, e . g ., to bind lithium ions in lithium component of each embodiment of the invention shown ion batteries , in graphene - nanoparticle hybrid batteries . where illustration is not necessary to allow those of ordinary Additionally , the carbonyl groups may be themselves func skill in the art to understand the invention . All patent 45 tionalized , thereby allowing for additional tuning of the applications and patents incorporated herein by reference are structural and / or electronic properties of the composition . incorporated by reference in their entirety . In case of con For example , amide functionalized materials may display flict, the present specification , including definitions, will expanded intersheet distances ( e . g . , in comparison to graph ite and chemically reduced graphene ) and /or high surface control. 50 areas, and may find application as supercapacitors . Addi DETAILED DESCRIPTION tional applications and uses and well as functionalization of the carbonyl groups are described herein . The present invention generally relates to compositions The methods and / or compositions described herein pro comprising functionalized carbon - based nanostructures vide numerous advantages and/ or improvements over cur such as functionalized graphene nanosheets, and related 55 rent methods and / or compositions . For example , while methods . Functionalized graphene -based materials and known methods for functionalizing graphene with carbon other carbon -based nanostructures may find use in many carbon bonds generally utilize either unstable colloidal applications , such as those described herein . Some embodi - solutions of preformed graphene nanosheets ( e . g . , arylation ments of the invention enhance the processability and /or methods ) or air and / or water sensitive metal- intercalated solubility of carbon - based nanostructures ( e . g . , graphene 60 graphite ( e . g ., alkylation methods ) , the methods described and graphene - based materials ) , for example , for use with herein generally utilize air and water (bench - stable ) graphite such applications . oxide (GO ) as the starting material for the chemical trans In some embodiments , the present invention provides formation . The methods and /or compositions also may com methods which allow for relatively large -scale production of prise high functional group densities , as described herein , functionalized graphene ( e . g . , graphene nanosheets ) using 65 which are generally higher than known methods / composi graphene oxide as the bulk starting material. Graphene oxide tions. In addition , the methods described herein can be will be known to those of ordinary skill in the art and conducted on large scales ( e .g ., kilotons of product) . Fur US 9 ,770 ,709 B2 thermore, many of the methods and systems discussed In one set of embodiments , R and R2 are both hydrogen ; herein are applicable not only to graphene oxide , but to other and R is OH . carbon -based nanomaterials as well , for example , carbon In one set of embodiments , R and R2 are both hydrogen ; nanotubes ( single or multi -walled ), fullerenes, or the like. and Rºis OMe or OEt. Further examples of carbon -based nanomaterials are 5 In some embodiments , the compositions and methods described in detail below . described herein comprise carbon -based nanostructures In some embodiments of the present invention , compo ( e . g ., graphene oxide and /or graphene) having a high density of functional groups . As used herein , a carbon -based nano sitions are provided . In some cases, the composition com structure having a “ high density of functional groups ” refers prises graphene or graphene oxide associated with at least 10 to carbon - based nanostructures comprising a plurality of one functional group . A functional group may be bound to functional groups attached to the surface of the nanostruc (e .g ., attached to ) the graphene network via a carbon -carbon ture , wherein the ratio of number of functional groups to bond ( e . g . , a carbon - carbon single bond ) , where one of the number of carbon atoms of the surface of the nanostructure carbon atoms forming the carbon -carbon bond is not itself is at least about 1 to 50 . The ratio may also be considered in part of the mesh or fused network of carbon atoms that 15 some embodiments as the surface density of functional defines the graphene network itself. Typically , the carbon groups on the surface of the nanostructure for a given unit atoms defining the graphene or graphene oxide network are area of the nanostructure , as defined by the number of arranged in a two- dimensional hexagonal or “ honeycomb ” . carbon atoms within that given unit area . In some cases, the structure . In some cases , the functional group bound to the ratio of functional groups to carbon atoms of the surface of graphene network comprises a carbonyl group . 20 the nanostructure is at least about 1 to 25 , at least about 1 to In some embodiments , the at least one functional group 20 , at least about 1 to 15 , at least 1 to 10 , at least about 1 to associated with graphene or graphene oxide has the struc 9 , at least about 1 to 8 , at least about 1 to 7 , at least about ture : 1 to 6 , at least about 1 to 5 , at least about 2 to 5 , or, in some cases , at least about 1 to 4 . Those of ordinary skill in the art will be aware of methods and systems for determining the ratio of functional groups to carbon atoms of the surface of the nanostructure . In some embodiments, methods are provided for forming functionalized carbon -based nanostructures ( e . g . , function 30 alized graphenes or functionalized graphene oxides ) . In some cases, the functionalized carbon - based nanostructure wherein R ', R2, and R3 can be the same or different, and is formed utilizing graphene oxide as a starting material . each is individually hydrogen or another suitable substitu - Graphene oxide may be chemically converted to a highly ent, optionally substituted , and G comprises a carbon atom functionalized form of graphene or graphene oxide , in which of the graphene or graphene oxide . In some embodiments , G 35 at least a portion of the carbon - oxygen chemical bonds of the comprises a carbon atom positioned within the basal plane graphene oxide are transformed into carbon - carbon bonds . of the graphene or graphene oxide ( e . g . , G is an interior In some cases , an allylic alcohol functional group ( e . g ., a carbon atom of the fused network of graphene or graphene hydroxyl group with an adjacent olefinic double bond two oxide ) . The term “ substituent” as used herein will be under - carbon atoms away ) commonly found on a graphene oxide stood by those of ordinary skill in the art and refers to all 40 surface is converted into an allylic carbon - carbon bond . In permissible substituents of the structure being referred to , some cases, the allylic functional group alcohol is converted " permissible ” being in the context of the chemical rules of into an allylic carbon - carbon bond via an intermediary valence known to those of ordinary skill in the art . In some functional group , for example , an allylic vinyl ether , an cases , the suitable substituent may be a salt. The suitable allylic ester, an allylic amide, an allylic ketone, an allylic substituent may be an organic substituent or non - organic 45 ketene acetal, an allylic N , O - ketene acetal, a beta - keto substituent. allylic ester , an allylic silyl ketene acetal, an allylic lithium In some cases , R1 and R2 can be the same or different and enolate , an allylic sodium enolate , an allylic zinc enolate, or each are independently hydrogen , alkyl, heteroalkyl, an allylic glycolates . The intermediary allylic functional cycloalkyl, alkenyl, or aryl, any of which is optionally groups can undergo a rearrangement ( e . g . , a sigmatropic substituted . In some embodiments , R and R2 are both 50 rearrangement ), in which the carbon -oxygen bond is broken , hydrogen . In some cases , R * is hydrogen , alkyl, aryl, alk - the carbon -carbon allylic double bond shifts over one bond , enyl, cycloalkyl , heteroalkyl, heteroaryl , N (R4 ) 2 SR4, and a new carbon - carbon single bond is formed on the Si( R4 ) 2, OR , or OM , any of which is optionally substituted , graphitic surface. A variety of pendant functional groups wherein M is a metal or cationic species and R4 is a suitable may be generated associated with the graphene or graphene substituent ( e . g . , hydrogen , an organic substituent , a metal- 55 oxide via a carbon - carbon ( e . g . , single ) bond depending on containing substituent) , optionally substituted . In some the reaction conditions and the reagents employed . For cases , each R can be the same or different and are hydrogen , example , graphene may be functionalized with moieties alkyl, cycloalkyl, haloalkyl, heteroalkyl , aryl, heteroaryl, or including aldehydes , carboxylic acids, esters, amides, and OH , any of which is optionally substituted . In some cases, ketones . at least one of R1, R², or R * is haloalkyl. In a particular 60 The methods described herein may involve treating the embodiment, R * is OR + or N (R4 ) 2 . In some embodiments , graphene or graphene oxide with a reducing agent. For R4 is alkyl substituted with an unsubstituted or substituted example , following functionalization , any remaining unre aryl or an unsubstituted or substituted cycloalkyl . acted oxygen functionalities on the graphene or graphene In some cases , Rºis N ( CH3) 2 , NH - phenyl, NH - biphenyl , oxide ( e . g ., unreacted allylic OH groups, etc . ) may be NHCH ( C = CH ) , OH , OMe, OET, OM , where M is a metal 65 chemically reduced , for example , using reductants such as ion , OCH2( C = CH ) , OCH2CH2( 2 -bromophenyl ) , OCH sodium borohydride , lithium aluminum hydride , hydrazine , (adamantyl ) , or OCH _ C ( 4 -chlorophenyl )z . vitamin C (l - acsorbic acid ) , potassium hydroxide, thermal US 9 ,770 ,709 B2 10 annealing, or ammonia . In some embodiments , the carbon In some embodiments , the reactant is CH2C (OCH3 ) 3 . In carbon bonds formed during the chemical attachment of the some embodiments , the reactant is an allylic ketene . at least one functional group to the graphene may remain In some cases , a method for fabricating a functionalized intact during and following the reduction conditions. In carbon - based nanostructure ( e . g ., graphene) comprises pro some cases , the resulting structure after chemical reduction 5 viding a carbon -based nanostructure including a group hav is a highly reduced graphene or graphene oxide that is ing formula ( I ) : surface functionalized with a plurality of functional groups attached via carbon - carbon bond linkages . Various other chemicalmanipulations may also optionally 10 be performed . For example , alcohols such as primary alco hols ( e . g . , present as unreacted oxygen functionalities on the C = C2C3 reduced graphene surface as described above or comprised in a functional group ) may be reacted with a variety of electrophilic reagents . Alkylation and acylation of the alco - 15 wherein C ', C , and C3 are part of a fused network of aromatic rings within the carbon -based nanostructure and hol groups may be performed in some embodiments , for OR is a pendant group of the fused network of aromatic example, via reaction of the modified reduced graphene with rings, wherein R is hydrogen or another suitable substitu alkyl halides and acyl halides, respectively . Alkylation with ent, optionally substituted . In some embodiments , R is perfluorinated alkyl halides may be performed , in other hydrogen , metal, alkyl, aryl , heteroalkyl, cycloalkyl, or embodiments . The pendant alcohol groups may also readily 20 oxygen - protection group , any of which is optionally substi react with epoxides to form beta -hydroxy ethers . tuted . In particular embodiments, RS is hydrogen . The car In some embodiments , the method comprises providing a bon - based nanostructure may be reacted with a reactant to carbon -based nanostructure comprising an allylic functional produce a group having formula ( II ) : group (e . g. , as may be present in graphene or graphene 25 oxide ) . The carbon -based nanostructure may be reacted with a reactant comprising at least one carbon atom to form a (II ) carbon - carbon bond between the at least one carbon atom PS within the reactant and a carbon atom within the carbon çt = 0 based nanostructure . The term “ allylic functional group , " as 30 used herein in connection with a carbon -based nanostruc R6 ture , refers to an allylic group which is a portion of the • cºcº = c , carbon -based nanostructure . Those of ordinary skill in the art will understand the term allylic functional group as wherein Rº, R ' , and Rºcan be the same or different, and referring to a hydroxyl group or an OR group ( R being a 35 each is independently selected from hydrogen or another suitable substituent, including , but not limited to , alkyl, suitable substituent, optionally substituted . In some cases, R6 and R7 can be the same or different and each are heteroalkyl, aryl, heteroaryl , etc ., optionally substituted ) independently hydrogen , alkyl, heteroalkyl, cycloalkyl, alk with an adjacent olefinic double bond two carbon atoms enyl, aryl, any of which is optionally substituted . In some away, for example , having structures such as : 40 cases, Rºis hydrogen , alkyl, aryl, alkenyl, cycloalkyl, het eroalkyl, heteroaryl, N (R4 ) , SR “ , Si( R4 ) , OR “ , or OM , any of which is optionally substituted , wherein M is a metal or OH cationic species and R4 is hydrogen or another suitable c = C2 - C3 or C — C2 - C3 — OR , substituent, optionally substituted . In a particular embodi 45 ment, R8 is OR + or N (R4 ) , . In some cases , each R4 can be the same or different and are hydrogen , alkyl, cycloalkyl, wherein C ' , C ', and Cºare part of the carbon -based nano - haloalkyl, heteroalkyl, heteroaryl, aryl, or OH , any of which structure ( e . g ., the graphene carbon network ). In some embodiments , the allylic functional group is positioned In some embodiments , the formation of a compound of within the interior of the basal plane of the graphene or 50 formula ( II ) from a compound of formula (I ) ( e. g ., an allylic graphene oxide ( e . g . , not positioned at the edge or perimeter transposition ) involves a rearrangement reaction . For of the graphene or graphene oxide) . example , the allylic transposition may be a sigmatropic rearrangement ( e . g . , a Claisen type rearrangement) , a In some cases , the reacting step comprises reacting the nucleophilic substitution reaction , or a metal catalyzed reac carbon -based nanostructure with a reactant comprising at 55 tion . Those of ordinary skill in the art will be aware of least one carbon atom , and transforming the allylic func suitable reagents and reaction conditions ( e . g ., solvent con tional group into a second allylic functional group . That is , ditions, temperature conditions, etc . ) for carrying out a in some cases, the allylic group is associated with a first rearrangement reaction , in accordance with the invention . functional group (e . g. , OR ) and converted to a second allylic In some embodiments , the rearrangement is a traditional group comprising a second functional group (e . g ., OC ( R ' ) 2 60 Claisen rearrangement ( e . g . , wherein the reagent is phenyl C ( R " ) z ) . The second allylic group may undergo rearrange - vinyl sulfoxide , ammonium betaines ( e . g . 3 - ( trimethylam ment, thereby forming a carbon - carbon bond between the atm onio )acrylate )) . In some cases, the rearrangement is an least one carbon atom within the reactant and a carbon atom Ireland Claisen ( e. g ., wherein the reagents may include acyl within the carbon -based nanostructure ( e . g ., the first func - chloride , propanoyl chloride , and lithium hexamethyldisi tional group may be associated with Cº of the allylic group , 65 lazide ( e . g ., a base ) ) . In some cases , the rearrangement is a and the carbon - carbon bond may form between a carbon Johnson Claisen rearrangement ( e . g . , wherein the reagent atom of the second functional group and C ' ) . may be triethylorthoformate, trimethylorthoformate , propi US 9 , 770 , 709 B2 12 onic acid ( e . g . , an acid source )) . In some cases , the rear In some cases , the compound of formula ( III ) comprising rangement may be an Eschenmoser Claisen rearrangement, one of the following structures: ( e . g . , wherein the reagent is dimethylacetamide dimethyl acetal) . In other cases , the rearrangementmay be a Carroll Claisen 5 reaction ( e . g . , wherein the reagent is ethylacetoacetate ) , also referred to as a “ Carroll reaction ,” “ Carroll rearrangement, ” | R1L or “ decarboxylative allylation . ” The Carroll rearrangement RILRII FER! ! =C OL occurs when a ß -keto allyl ester undergoes a [ 3 , 3 ] sigma 10 tropic rearrangement to generate CO2 and an allyl ketone . allylic vinyl ether MECL RUL Typically , the B -keto allyl ester is heated , treated with base , or exposed to catalytic amounts of palladium . In some allylic ester embodiments , graphene or graphene oxides functionalized OR4 with ß -keto allyl esters may be generated by reaction of 15 NR4 RII graphene or graphene oxide with an acyl ketene, a high RII LRI energy intermediate . In an illustrative embodiment, FIG . 0 VRI ? Q =CI RII 15A shows the reaction of graphene oxide with an acyl Cz= ( 1 RIIÓ ketene to generate a B -keto allyl ester. Acyl ketenes can be allylic ketene acetal generated using various methods known in the art, as shown 20 allylic imidate in FIGS . 15B - D . One example is thermal fragmentation of acylated Meldrum ' s acid derivatives , Another example N (R4 ) 2 involves coupling of Meldrum ' s acid with an carboxylic RI acid by way of a peptide coupling reagent such as N , N . RULRil , or dicyclohexylcarbodiimide or diethyl cyanophosphate . Addi - 25 = ( tionally, acyl ketenes can be thermally generated from op =0 PRIROR1} dioxinone derivatives, as shown in FIG . 15C . In some cases, allylic N . O - ketene acetal the surface of graphene or graphene oxide may be exposed allylic beta -keto ester to a B -keto acid chloride and a non - nucleophilic base . OM In some cases, reacting the carbon - based nanostructure 30 with a reactant causes a group having formula ( I ) to be RII converted to a group having formula ( III ) : maal R11 (III ) 35 allylic metallo enolate (R41 ) n — _ — - — , wherein C ', C , and C3 are part of the carbon -based nano structure , and R ! ! , R4, and M are as defined herein . If more O 40 than one Rl is present in a structure, the two Rll moieties cl = c _ c . may be the same or different. In some cases, R4 is silicon , alkyl , heteroalkyl, alkenyl, or aryl, optionally substituted . wherein Rº, R10 , and Rl1 can be the same or different, and Those of ordinary skill in the art will be aware of suitable each is independently selected from hydrogen or another reagents for forming a compound of formula ( III) . suitable substituent, optionally substituted , or wherein Rº 45 In some embodiments , graphene oxide may be reacted and R10 are joined together to form = NR14 or = 0 , and R14 with CH C (OCHZ ) z to produce a vinyl- ether intermediate is hydrogen or another suitable substituent, optionally sub - that rearranges to produce the an allylic ester , as shown in stituted , n is 2 or 3 , and -- - - represents a single or double FIG . 14A . bond . The group having formula ( III ) may then be converted In some embodiments , graphene oxide may be reacted to a group having formula ( II) , for example , via a sigma - 50 with an acyl ketene ( e . g . , O = C = C — ( C = 0 ) - R ) to form tropic rearrangement. Generally , when the compound of a beta -keto -allyl ester, which can then rearrange to form an formula ( III) is rearranged to form a compound of formula allylic ketone , as shown in FIG . 15A . ( II ) , R8 is Rº or R10 , or a salt or protonated version thereof, Compositions described herein may find use in various and R7 and Ró is an Rll or a salt or protonated version applications. In addition , the association of a carbonyl group thereof. 55 with a carbon -based nanostructure via a carbon - carbon bond In some cases, each Rl1 can be the same or different and may allow access to further functionalize the carbon -based are hydrogen , alkyl, cycloalkyl , haloalkyl, heteroalkyl , alk - nanostructure , thus allowing for the tuning of the mechani enyl, aryl, heteroaryl , OH , OR + or CEO) R4 any of cal and /or structural properties of the carbon -based nano which is optionally substituted , wherein R4 is hydrogen or structures . In some cases , the spacings between graphene another suitable substituent, optionally substituted or as 60 sheets may be affected , at least in part, by the size, shape , defined herein . In some cases, Rº, R10 , and R14 are each chemical composition , and / or chemical affinity of the func independently hydrogen , alkyl, aryl, alkenyl, cycloalkyl, tional groups. For example , in some embodiments , if gra heteroalkyl, heteroaryl, N (R +) 2 , SR “ , Si(R4 ) 2, OR , or OM , phene oxide is used , the spacing between graphene layers any of which is optionally substituted , wherein M is a metal can be tailored based on the type of functionalization and ( e . g ., Na , Zn , K , Li, Ba , Ca ) or cationic species and each R + 65 substituents associated with the functional group . For can be hydrogen or another suitable substituent, optionally example , larger groups associated with the graphene ( e . g . , substituted , or as defined herein . R?- R8 in compound of formula ( II) ) may create larger US 9 , 770 , 709 B2 13 14 interlayer spacings . Additional components could be con - solid phase ) . For example , the binding site may be a func tained within the interlayer spaces and may provide func tional group , such as a thiol, aldehyde , ester, carboxylic acid , tions such as charge storage and/ or ion conduction . As a hydroxyl, or the like , wherein the functional group forms a specific example , graphite oxide ( i . e . , graphene oxide bond with the analyte . In some cases , the binding site may sheets ) has interlayer spacings of about 8 . 4 A , whereas 5 be an electron - rich or electron - poor moiety within the com graphene functionalized with CH , C (= O )NMe , groups has position , wherein interaction between the analyte and the interlayer spacings of about 9 . 3 Å . composition comprises an electrostatic interaction . For The ability to incorporate components between interlayer example , the composition may include an electron - donating spaces may be useful for energy storage applications such as group and the analyte may include an electron - withdrawing batteries , capacitors , etc . In some cases, the composition 10 group . Alternatively , the composition may include an elec may be used as cathodes and / or anodes materials in batter tron - withdrawing group and the analyte may include an ies , or as a material in capacitors . Thus, in some embodi- electron - donating group . ments , the spacing between carbon -based nanostructures The composition may also be capable of biologically ( e . g . , graphene sheets ) can be controlled by and/ or tailored binding an analyte via an interaction that occurs between though the size , shape , chemical composition , and/ or chemi- 15 pairs of biological molecules including proteins , nucleic cal affinity of the functional groups associated with the acids, glycoproteins , carbohydrates, hormones , and the like . carbon -based nanostructure . In some embodiments , the Specific examples include an antibody / peptide pair , an anti functional groups may increase the ability of the carbon - body /antigen pair , an antibody fragment/ antigen pair , an based nanostructure material to associate with and / or store antibody / antigen fragment pair , an antibody fragment/ anti redox active species ( e . g . , between interlayer spaces ) . In 20 gen fragment pair , an antibody/ hapten pair , an enzyme some cases, the redox active species may be lithium . In some substrate pair , an enzyme/ inhibitor pair , an enzyme/ cofactor cases , the composition may be used to store charge , e . g . , by pair , a protein /substrate pair , a nucleic acid /nucleic acid pair, incorporating the material into a charge storage device. In a protein /nucleic acid pair, a peptide/ peptide pair, a protein / some cases , the charge storage device is a capacitor and /or protein pair , a small molecule /protein pair , a glutathione / an electrochemical double layer capacitor. 25 GST pair, an anti -GFP /GFP fusion protein pair , a Myc /Max The properties of the compositions described herein may pair , a maltose /maltose binding protein pair , a carbohydrate / be tuned based on the substitution of the carbonyl functional protein pair, a carbohydrate derivative /protein pair , a metal group . Those skilled in the art would recognize what types binding tag /metal / chelate , a peptide tag/ metal ion -metal of functional groups would afford a particular, desired chelate pair , a peptide/ NTA pair , a lectin / carbohydrate pair , property , such as the ability to act as a filter or to determine 30 a receptor/ hormone pair , a receptor/ effector pair , a comple an analyte or other species . In one set of embodiments , the mentary nucleic acid / nucleic acid pair , a ligand / cell surface composition may be functionalized with a binding site for receptor pair , a virus/ ligand pair , a Protein Alantibody pair, determination of a target analyte . For example , a sample a Protein G / antibody pair , a Protein L /antibody pair , an Fc suspected of containing an analyte may be exposed to a receptor/ antibody pair , a biotin / avidin pair, a biotin / strepta composition as described herein . The analyte may interact 35 Vidin pair , a drug / target pair , a zinc finger/ nucleic acid pair , with the composition to cause a change in a property of the a small molecule /peptide pair , a small molecule / protein pair , composition , such as an optical property or an electrochemi- a small molecule / target pair , a carbohydrate/ protein pair cal property , wherein the change in the property may then such as maltose /MBP (maltose binding protein ) , a small determine the analyte . As used herein , the term “ determi- molecule / target pair , or a metal ion / chelating agent pair . nation ” or “ determining” generally refers to the analysis of 40 In some cases , the carbonyl functional groups may be a species or signal, for example , quantitatively or qualita - further functionalized to incorporate functional groups tively , and /or the detection of the presence or absence of the capable of undergoing redox reactions ( e . g . , conducting species or signals. “ Determination ” or “ determining " may polymer ) , which may lead to enhancement of the charge also refer to the analysis of an interaction between two or storage of these compositions. For example , bound amides more species or signals , for example , quantitatively or 45 may produce cyclic structures wherein the oxygen binds to qualitatively , and /or by detecting the presence or absence of cationic charges in a graphene layer that delocalizes the the interaction . charge onto the nitrogen atoms and can thereby enhance the In some embodiments , the interaction between the com - charge storage capabilities of the graphene . FIG . 9 shows an position and an analyte may comprise formation of a bond , illustrative embodiment, where an oxidized graphene sheet such as a covalent bond ( e . g . carbon - carbon , carbon - oxygen , 50 functionalized with amide groups may undergo a redox oxygen - silicon , sulfur - sulfur, phosphorus - nitrogen , carbon reaction such that charge from the graphene layer is delo nitrogen , metal- oxygen or other covalent bonds) , an ionic calized onto the amide nitrogen . bond , a hydrogen bond ( e . g . , between hydroxyl, amine , Accordingly , in some embodiments , the carbonyl species carboxyl, thiol and / or similar functional groups, for may be functionalized with an electrochemically active example ), a dative bond ( e . g . complexation or chelation 55 functional group . Non - limiting examples of electrochemi between metal ions and monodentate or multidentate cally active functional groups include conducting polymers , ligands ) , or the like . The interaction may also comprise Van metals , semi-metals , and / or semiconductors . In some cases , der Waals interactions . In one embodiment, the interaction the functionalization contains amides which can form cyclic comprises forming a covalent bond with an analyte . The structures with the carbon -based nanostructure , wherein the binding site may also interact with an analyte via a binding 60 Oxygen binds to cationic charges in the carbon nanostruc event between pairs of biological molecules . For example , ture . In some cases , the electrochemically active species is the composition may comprise an entity , such as biotin that a species typically used in batteries and would be readily specifically binds to a complementary entity , such as avidin identified by those skilled in the art . or streptavidin , on a target analyte . In some embodiments , the composition may be appropri In some cases, the composition may comprise a biological 65 ately functionalized to impart desired characteristics (e . g ., or a chemical molecule able to bind to another biological or surface properties ) to the composition . In some embodi chemicalmolecule in a medium ( e . g . , solution , vapor phase , ments , the composition may include compounds , atoms, or US 9 ,770 ,709 B2 15 16 materials that can alter or improve properties such as com - tageously evaluated in accordance with the embodiments patibility with a suspension medium ( e . g ., water solubility , described herein . In some cases the sample is a vapor phase water stability ) , photo - stability , and biocompatibility . In sample drawn or derived from a composition or device some cases, the composition comprises functional groups comprising nicotine ( e . g ., a cigarette ) . In some cases, the selected to possess an affinity for a surface . For example , the 5 sample may be drawn from a water supply . composition may also be functionalized to facilitate adsorp - For example , the method may involve contacting a vapor tion onto a particular surface , such as the surface of a phase sample containing a first concentration of the species substrate . In some embodiments , the composition is func - with a composition comprising substituted graphene or tionalized with carboxylic acid moieties , which may allow graphene oxide molecules . Upon contacting the concentra for electrostatic adsorption onto charged surfaces , such as 10 tion , the vapor phase sample may have a second , decreased glass surfaces , particle surfaces , and the like . concentration of the species . In some embodiments , the In some cases , the carbonyl species may be functionalized concentration of the species may be reduced by at least 5 % , such that the graphene material is at least partially or at least 10 % , at least 20 % , at least 30 % , at least 40 % , at least substantially water - soluble . Examples include embodiments 50 % , at least 60 % , at least 70 % , at least 80 % , at least 90 % , where the functional groups are — CH , C ( = O )NMe , or 15 at least 95 % , or, in some cases , at least 99 % . - CH2CO OR ", where R9 is hydrogen , alkyl, alkenyl, Without wishing to be bound any theory, the functional alkynyl, or aryl, any of which is optionally substituted , In i zed graphenes or graphene oxides described herein may be some embodiments , the functional groups may be saponified particularly effective in the removal or reduction in the to form _ CH _ COH groups or a salt thereof. In such amount of a substance in sample as the intersheet distance embodiments , the pH of a resulting solution of the graphene 20 between adjacent graphene or graphene oxide molecules may be increased or decreased , thereby causing the carbox may be advantageously varied ( e . g ., increased , decreased ) to ylic acid moieties to be either protonated or unprotonated . In suit a particular application , based on the functionalization some cases , the ability to alter between protonated and on the basal plane of the graphene or graphene oxide sheets . unprotonated forms of the graphene may aid in the purifi- For example , the graphene or graphene oxide sheets or may cation , solubility , and / or stability of the graphene . For 25 exhibit increased surface area to due at least in part to an example , the protonated form may be substantially insoluble increase in intersheet distance between graphene molecules in water and /or layers of the graphene may associated with or graphene oxide molecules. This may be attributed to each other , such that small colloids and / or clusters of the functionalization on the basal plane of the graphene or graphene may form . In the unprotonated form , each gra - graphene oxide sheets by sterically large functional groups , phene sheet may comprise a plurality of negative charges , 30 and may advantageously allow for increased interaction such that the graphene is soluble or substantially soluble in (e . g ., van der Waals interactions ) between the composition water and /or each graphene layer is not associated with any and the sample . In some embodiments , the functional groups other layers or graphene materials ( e . g . , due to electrostatic may be selected to have a particular size to produce an repulsions of the layers ) . For example , see FIGS. 8 and 13 intersheet distance capable of trapping or sequestering a for illustrated examples of this process . Such a transition 35 particular analyte or species within the composition . The ( e . g . , from substantially soluble or soluble , to substantially ability to covalently functionalize graphene or graphene insoluble or insoluble ) may aid in purification of the material oxide sheets with a wide array of groups, as described ( e . g . , by filtration , washing , etc . ) . Those of ordinary skill in herein , may also be advantageous as the compositions may the art will be aware of methods for saponifying amides be tailored for specific targets . For example , functional ( e . g . , in the presence of a base at elevated temperatures , for 40 groups which have known specific interactions with poten example , KOH in EtOH / H , O at reflux ) . tial contaminants may be appended onto graphene or gra Some embodiments provide stable , aqueous colloids or p hene oxide sheets, thereby turning the graphene or gra emulsions comprising graphene species capable of remain - phene oxide sheet into a “ super- ligand ” for a wide range of ing in solution without the need for polymeric or surfactant substances, including toxic materials. Examples of such stabilizers . The graphene species may be substituted , for 45 substances and samples are described herein . As an illustra example , on the basal plane by allylic carboxylate groups. In tive embodiment, a chelator such as dimercaprol or its some embodiments , the stability of an emulsion and /or analogs may be attached to a graphene or graphene oxide colloidal suspension may be determined based on the zeta sheet in order to trap heavy metals ( e . g . , Cd . potential of the emulsion and /or colloidal suspension . Gen - In some embodiments , the compositions may be used to erally, emulsion /colloidal suspension having a zeta -potential 50 selectively absorb , trap , and/ or filter chemicals ( e . g ., gases of about + 40 mV or greater are considered to have good and /or liquids ) . For example , the carbon -based nanostruc stability . In some cases , the zeta -potential of the emulsion or ture may be functionalized with groups such as perfluoro colloid may be about £20 mV, about + 30 mV, about + 35 mV, alkyl groups and /or nitroaromatic groups, which may inter about + 40 mV, about + 45 mV, about 250 mV, about 255 mV, act with ( e . g ., bind ) toxins , pollutants , or other undesirable about +60 mV, about 365 mV, about 170 mV, or greater. 55 materials . The interaction may include an electrostatic inter In some cases , the compositions may include positively action ( e . g . , between relatively electron - rich moieties of a and / or negatively charged functional groups. chemical and relatively electron - poor moieties of a carbon The compositions and materials described herein may based nanostructure ) , a non - covalent interaction ( e . g . , bind serve as effective substrates for reducing the amount of, or i ng interaction ) , a covalent interaction , or the like . In an even removing , a substance ( e . g . , toxic compounds ) from a 60 illustrative embodiment, the carbon - based nanostructure sample . In some cases , the sample is a vapor phase sample . may include a plurality of electron - poor nitroaromatic In some embodiments , the sample is a liquid sample . In groups capable of interacting with ( e . g . , binding ) electron some embodiments , the sample is an aerosol sample . The rich groups of an organic pollutant via the nitroaromatic term “ sample ” refers to any material ( e . g ., in vapor phase, groups. In some embodiments , the composition may include liquid phase , solid phase , aerosols, etc . ) containing a species 65 orbitals ( e . g . , p - orbitals ) that may sufficiently overlap with to be determined ( e . g . , an analyte ) , purified , filtered , orbitals present on a particular analyte . For example , the absorbed , adsorbed , chemically altered , or otherwise advan - interaction may involve pi- pi stacking between conjugated US 9 ,770 ,709 B2 17 18 pi- system of a high surface area graphene or graphene oxide nide, and others. In some embodiments , the analyte is carbon with polycyclic aromatic hydrocarbons, including undesir monoxide. In some embodiments , the analyte is a heavy able components of cigarette smoke , such as benzopyrene . metal. In some cases, the analyte may be a metal ion ( e . g ., a heavy In one set of embodiments , the compositions described metal ion ) having d -orbitals which overlap with the pi- 5 herein may be useful as cigarette filter materials . (FIG . 20 ) system of the functionalized graphene or graphene oxide For example , the composition may be arranged in a ciga rette , or related product or device containing nicotine , and sheets and / or various carbonyl groups on the graphene or the sample contacting the composition may be vapor gen graphene oxide sheets . Thus, compositions described herein erated by the cigarette , i . e . , cigarette smoke . The composi may be useful for removing undesired chemicals from fluids 10 tion may be effective in reducing the amount of undesirable or liquids . substances found in cigarette smoke, including analytes as In some embodiments , a composition described herein is described herein . used in a device which functions as a filter , catalyst, and / or Compositions described herein may also be appropriately sensor . functionalized to serve as catalysts or as a support material In some embodiments , a device for filtering or reducing 15 for catalysts . In some cases , the functional groups comprise the amount of a substance ( e. g ., a toxin , pollutant) in a catalytic metals or metal- containing groups , such as metal sample may comprise a composition described herein . The oxides . In certain cases, the functional groups comprise device and /or composition may be contacted with a sample positively and /or negatively charged functional groups containing an undesired substance , such as a toxin . The which may bind metal ions capable of operating as catalysts . substance may be introduced to a device comprising the 20 In some cases, the functional groups function as metal composition , and the composition may interact with the binding ligands , or ligands for metal- containing groups, and substance such it reduces the amount of the substance that comprise nitrogen , sulfur, and/ or phosphorus , thereby allow exits the device . In some cases, prior to contact with the ing the materials to function as a catalyst . In some embodi device and / or composition , the sample may have a first ments , the bound metal or metal- containing group ( e . g . , concentration of a substance , and , after contacting the device 25 metal oxide ) may be used for the reduction of oxygen ( e . g ., and / or composition , the sample may have a second concen in a fuel cell ). In certain cases, the bound metal may oxidize tration of the substance , which is less than the first concen - and /or reduce water to make oxygen and /or hydrogen gases. In some embodiments, the functional group may comprise a tration . For example , the composition may physically pre species capable of reducing or oxidizing various species, vent the substance from diffusing away from th the 30 including oxygen . Without wishing to be bound by any composition by binding or otherwise interacting with the theory , covalent functionalization of graphene or graphene substance . In some embodiments, the composition may oxide sheets on the basal plane may be advantageous in that interact with the substance to chemically alter the substance the available surface area of the graphene would be altered or convert the substance into a more desirable species , as ( e . g . , increased , decreased ) , allowing for enhanced interac described more fully below . 35 tion with an analyte or other sample . Additionally , the In some cases , the device filters, chemically alters, and /or composition includes covalent, and relatively robust , attach senses analytes and other species including pollutants , tox ment between the catalyst and the graphene or graphene ins , and other undesirable substances . In some cases, the oxide sheets , potentially resulting in a more stable system analyte includes functional groups containing perfluoro - and /or enhanced catalytic rates. alkyls or nitroaromatics . In some embodiments, the device 40 As an illustrative embodiment, the compositions may filter and /or sense nitroaromatic molecules and other described herein may be used for oxidation of carbon electron - poor molecules with electron - rich functional monoxide to carbon dioxide . For example , a functionalized groups . graphene or graphene oxide containing a catalyst ( e . g . , metal The analyte or species may be a chemical or biological catalyst ) may be prepared using methods described herein . analyte . The analyte or species may be any chemical, 45 Carbon monoxide may interact with the catalyst attached to biochemical, or biological entity ( e . g . a molecule ) to be the graphene or graphene oxide sheet and undergo the analyzed , including organic species , metal- containing spe- catalytic cycle to CO , . In some cases , the composition ( e . g ., cies, metals and metal ions, or other inorganic species . In a composition comprising a Pd catalyst ) may also be capable some cases , the composition may be selected to have high of reducing nitric oxide concurrently with oxidizing CO . specificity for the analyte . In some embodiments, the analyte 50 Such methods may be useful , for example , in treating or comprises a functional group that is capable of interacting filtering cigarette smoke to remove CO and /or NO . Those of with at least a portion of the composition , such as a ordinary skill in the art would be able to select various functional group positioned on a basal plane of a graphene catalytic moieties capable of oxidizing CO for use in the or graphene oxide sheet. For example , the functional group context of the embodiments described herein . In some cases , may interact with the analyte by forming a bond, such as a 55 the catalytic moiety comprises Pd , Fe , Ce, Al, Cu , or Ti , or covalent bond or a non - covalent bond . In some embodi - an oxide thereof . Examples of catalysts for CO oxidation ments , the functional group may interact with the analyte by include , but are not limited to , Pd nanoclusters, Fe203 , chemically altering the analyte . Some embodiments involve FOOH , or TiOOH . analytes comprising electron -withdrawing groups such as In some cases, the functional group is capable of binding perfluoroalkyl groups and/ or nitroaromatic groups . 60 a metal atom or ion , and comprises nitrogen , sulfur , and / or Examples of analytes and species include, but are not phosphorus . In certain embodiments , the compositions limited to , various toxins, pollutants , such as tobacco - spe described herein are used in a fuel cell. In some instances , cific N -nitrosamines ( TSNAs ) , hydrocarbons such as ben compositions described herein are used for the reduction of zene or benzopyrene , pesticides , formaldehyde , metals water. including toxic metals , heavy metals , and / or radioactive 65 In some embodiments , the composition may be employed metals such as arsenic , cadmium , lead 210 , and the like , in composites for mechanical property enhancement. For gases such as ammonia , carbon monoxide , hydrogen cya example , this may be accomplished either through a cova US 9 ,770 ,709 B2 20 lent linking of the carbon -based nanostructure ( e . g . , gra as an electron donor while the carbon -based nanostructure phene ) to the matrix or through functionalization of the may act as the electron acceptors, wherein the carbon -based carbon - based nanostructure that allows for the carbon -based nanostructures enhance the electron mobility through the nanostructures to be dispersed throughout the matrix mate - device , resulting in photovoltaic devices having improved rial. Additionally the functionalization of the carbon -based 5 performance . nanostructure may be used to produce composites which are Compositions described herein may be useful in other formed substantially from graphene or graphene oxide , applications, including chemical sensors , transistors ( e . g . , wherein the graphene or graphene oxide sheets are associ organic transistors ) , transparent conductive coatings, elec ated with each other ( e . g . , via the functional groups ) . trodes ( e . g . , for electrocatalysis ), components in photovol Accordingly , in some embodiments , compositions 10 taic devices, light- emitting diodes ( e. g . , OLEDs, PLEDs, described herein may be arranged in a composite material etc . ) , semiconductors , reinforcing elements for polymers comprising a matrix material. In some cases, the carbon - including high strength polymers , composites, displays, based nanostructures are associated with the matrix material actuators ( e . g . , polymer mechanical actuators ) , energy stor via at least one covalent bond . In certain embodiments , the age / production , circuits , flame retardantmaterials , and emis covalent bond is form via an epoxide , amine , and / or ure - 15 sive elements . In some cases , the compositions may be thane chemistries known to those skilled in the art. In some useful in cosmetic compositions . In certain embodiments , cases, a carbon - based nanostructure is functionalized such the compositions may exhibit ion exchange properties and that the material can be dispersed through the matrix mate may be useful in water purification . Many other applications rial. In some embodiments , the functional groups of the could benefit from the methods and compositions described carbon - based nanostructure are compatible and / or the same 20 herein , including electronic materials for the semiconductor as the functional group of the matrix material. In certain industry , gas- transport barrier agents for thermoplastic and instances , the functionalization has a negative Flory inter - thermoset resins ( e . g . , for food and beverage packaging ) , action parameter with the matrix material. In some embodi - flame retardants , additives for automotive fuel lines and gas ments , a carbon -based nanostructure is linked to a second tanks ( e . g ., as electrostatic discharge protection ) , additives carbon - based nanostructure via the functional groups of 25 for increased modulus and electrical conductivity ( e . g . , for each of the carbon -based nanostructures . electrostatic painting ) in automotive body panels , conduc Those of ordinary skill in the art will be aware of various tive adhesives, and electrode materials for rechargeable additional applications in which the compositions described batteries and capacitors herein may be employed and various methods and tech According to certain embodiments of the invention , a niques for processing and forming devices comprising the 30 graphene dispersion or other dispersion using carbon -based compositions provided herein . nanostructures such as those discussed herein may be used The compositions described herein may also be useful as in the application of thin coatings which could produce biological imaging agents, medical diagnostic agents , or flexible , conductive , transparent electrodes (i . e . replace biosensors . For example , carbon -based nanostructures com ments for indium tin oxide coatings ), conductive barrier in prising charged moieties may be useful as DNA diagnostics , 35 OLED and organic photovoltaic (OPV ) devices, non -halo wherein selection of the charged moieties may modulate genated fire retardant coatings, as well as electrostatic dis interaction of the carbon - based nanostructures with DNA charge protection for plastics , e . g . , due to the ability to molecules . The carbon - based nanostructures may be func - control the spacing of such nanostructures within a material. tionalized to increase or decrease electrostatic interactions of Products such as moisture and oxygen barrier sealants for the composition with DNA . In some cases , the carbon -based 40 the organic photovoltaic (PV ) and light emitting diode nanostructures may be assembled in combination with markets can also be produced in some cases. Charge storage enzymes , or other biomolecules, for sensing applications . devices such as ultracapacitors and rechargeable batteries In another set of embodiments , the composition may be can be produced that use graphene or other compositions as useful in coatings ( e . g . , electrostatic assembly ) . For described herein , e . g . , as electrodes , in accordance with example , a composition may be associated with a comple - 45 certain embodiments of the invention . The ability to chemi mentarily charged material ( e . g ., polymer, DNA , RNA , cally exfoliate and modify the surface of certain graphene proteins, inorganic particles / clusters , individual metal ions structures and reassemble the modified structures into a bearing multiple charges , carbon nanotubes , fullerenes , gra - layered structure with specific inter - planar spacing may be phene , etc .) . For example , the complementarily charged used within such energy - storage devices , e . g ., by allowing material may be positively charged and the composition may 50 ions to be contained within such layered structures . In comprise negatively charged moieties , such the composition certain embodiments , the ability to controllably functional associated with the material and forms a coating on the ize the surface of certain graphene structures, and / or their material. In some cases , the coating may substantially spacing , allows the structures to be dispersed into a plastic encapsulate the material. or a polymer to modifying its strength , fracture toughness, In some cases, the compositions may be used in optical 55 heat distortion temperature , moisture or oxygen diffusivities , applications. In some embodiments , the compositions may and /or conductivities ( both thermal and electrical) . For have anisotropic structures that may interact with light ( e . g ., example , a particular spacing of graphene structures may be polarized light ) selectively and give rise to polarized depen - selected in order to cause a polymer containing the graphene dent properties . structure to exhibit a certain ionic or electrical conductivity In another set of embodiments , functionalized carbon - 60 therein . based nanostructure may be useful as electron transport The methods of forming functionalized carbon -based materials in photovoltaic devices . The functionalized car - nanostructures and/ or various embodiments described bon -based nanostructure may be combined with a material herein may be carried out in any suitable solvent, or com such as a conducting polymer , wherein the carbon - based bination thereof. Examples of solvents that may be suitable nanostructure are functionalized with functional groups 65 for use in the invention include , but are not limited to , facilitating the stable formation of polymer blends, as benzene, p - cresol, toluene , xylene , mesitylene , diethyl ether , described herein . In operation , the polymer matrix may act glycol, petroleum ether , hexane , cyclohexane , pentane , US 9 ,770 ,709 B2 21 dichloromethane (or methylene chloride ) , chloroform , car In some cases, the carbon -based nanostructure has an bon tetrachloride , dioxane , tetrahydrofuran ( THF ) , dimethyl average maximum cross - sectional dimension of no more sulfoxide , dimethylformamide , hexamethyl- phosphoric tri- than about 1000 nm . In some cases , however, the maximum amide , ethyl acetate , pyridine, triethylamine , picoline, mix cross -sectional dimension may be greater than about 1000 tures thereof , or the like . The methods described herein may 5 nm , for example , the carbon -based nanostructure has an be carried out at any suitable temperature ( s ) . average maximum cross- sectional dimension of no more In some cases , the reaction is carried out at about room than about 1 um , about 2 um , about 3 um , about 4 um , about temperature ( e . g ., about 25° C . , about 20° C . , between about 5 um , about 10 um , or greater. In some embodiments, the 20° C . and about 25° C ., or the like ) . In some casesases, , carbon -based nanostructure may comprise at least about however , the reaction may be carried out at a temperature 10 30 % , at least about 40 % , at least about 50 % , at least about below or above room temperature, for example , at about 60 % , at least about 70 % , at least about 80 % , at least about - 70° C ., about – 50° C . , about - 30° C ., about - 10° C ., about 90 % , or at least about 95 % of carbon by mass , or more . As - 0° C ., about 10 °C ., about 30° C ., about 40° C ., about 50° used herein , the “ maximum cross -sectional dimension ” C . , about 60° C ., about 70° C . , about 80° C . , about 90° C . , refers to the largest distance between two opposed bound about 100° C ., about 120° C . , about 140° C . , or the like . In 15 aries of an individual structure that may be measured . some embodiments , the reaction may be carried out at more In some cases, the carbon - based nanostructure may com than one temperature ( e . g ., reactants added at a first tem - prise a nonplanar portion , e . g . , a curved portion having a perature and the reaction mixture agitated at a second convex surface and a concave surface (where “ surface , ” in wherein the transition from a first temperature to a second this context, defines a side of a molecule or sheet defining a temperature may be gradual or rapid ) . 20 carbon -based nanostructure ) . Examples of carbon - based A reaction may be allowed to proceed for any suitable nanostructures comprising non -planar portions include period of time. In some cases , the reaction is allowed to fullerenes , carbon nanotubes , and fragments thereof, such as proceed for about 10 minutes , about 20 minutes , about 30 corannulene . In some cases , the nonplanar aromatic portion minutes, about 40 minutes, about 50 minutes , about 1 hour , may comprise carbon atoms having a hybridization of sp2. * , about 2 hours , about 4 hours , about 8 hours , about 12 hours , 25 wherein x is between 1 and 9 , i . e . , the carbon atom may have about 16 hours , about 24 hours , about 28 hours , or the like. hybridization between sp² - and sp - hybridization , where this In some cases, aliquots of the reaction mixture may be hybridization is characteristic of non - planarity of the mol removed and analyzed at an intermediate time to determine ecule as would be understood by those of ordinary skill in the progress of the reaction . the art . In these embodiments , x can also be between 2 and As used herein , a “ carbon - based nanostructure ” refers to 30 8 , between 3 and 7 , or between 4 and 6 . x may also be 1 , 2 , a carbon - containing structure comprising a fused network of 3 , 4 , 5 , 6 , 7 , 8 , or 9 , or fractions thereof. Typically , planar rings , such as aromatic rings . In some embodiments , the aromatic groups and polycyclic aromatic groups ( e . g . , phe carbon -based nanostructure comprises a fused network of at nyl , naphthyl) may comprise carbon atoms having sp least 10 , at least 20 , at least 30 , at least 40 , or, in some cases , hybridization , while non - aromatic , non - planar groups ( e .g . , at least 50 rings , at least 60 rings , at least 70 rings, at least 35 alkyl groups ) may comprise carbon atoms having spor 80 rings , at least 100 rings , or more . The carbon - based hybridization . For carbon atoms in a nonplanar aromatic nanostructure may be substantially planar or substantially group , such as a nonplanar portion of a carbon -based nano non - planar, or may comprise planar and /or non - planar por - structure , spa -hybridized carbon atoms may be distorted tions . The carbon - based nanostructure may optionally com - ( e . g . , bent) to form the nonplanar or curved portion of a prise a border at which the fused network terminates . For 40 carbon -based nanostructure . Without wishing to be bound example , a sheet of graphite is a planar carbon -based nano - by theory , this distortion may cause angle strain and may structure comprising a border at which the fused network alter the hybridization of the carbon atoms. As a result , the terminates , while a fullerene is a nonplanar carbon - based reactivity of the strained carbon atoms may be enhanced . nanostructure which lacks such a border. In some cases , the In some cases , the carbon - based nanostructure may com border may be substituted with hydrogen atoms. In some 45 prise an elongated chemical structure having a diameter on cases , the border may be substituted with groups comprising the order of nanometers and a length on the order ofmicrons oxygen atoms ( e . g . , hydroxyl) . In other cases , the border ( e . g . , tens or microns , hundreds of microns , etc . ) , resulting may be substituted as described herein . The term “ fused in an aspect ratio greater than 10 , 100 , 1000 , 10 , 000 , or network ” does not include , for example , a biphenyl group , greater . In some cases, the carbon - based nanostructure may wherein two phenyl rings are joined by a single bond and are 50 have a diameter less than 1 um , less than 100 nm , 50 nm , less accordingly not fused together . Two rings are “ fused ” when than 25 nm , less than 10 nm , or, in some cases , less than 1 there is at least one atom present within the structure that can nm . For example , the carbon - based nanostructure may have be simultaneously thought of as integrally defining each of a cylindrical or pseudo - cylindrical shape ( e. g . , carbon nano the two rings. In some cases, the fused network may tube ) . substantially comprise carbon atoms. In other cases , the 55 In some cases, the carbon -based nanostructure comprises fused network may comprise carbon atoms and heteroatoms. graphene ( e . g . , graphene nanosheets ) . As used herein , the Some examples of carbon -based nanostructures include gra - term “ graphene” is given its ordinary meaning in the art and phene , carbon nanotubes ( e . g . , single -walled carbon nano - refers to polycyclic aromatic molecules in which a plurality tubes (SWCNTs ) , multi -walled carbon nanotubes (MW - of carbon atoms is covalently bound to each other . The CNTs ) ) , fullerenes, and the like , as describe more herein . 60 covalently bound carbon atoms form repeating units that Also , as noted above , other carbon -based materials ( e . g . comprise 6 -membered rings , but can also form 5 -membered which may not necessarily comprise nanostructures) , such rings and /or 7 -membered rings . Accordingly , in graphene it as carbon fibers, carbon fiber paper , activated carbon , and appears as if the covalently bound carbon atoms (usually , sp ? other materials that comprise carbon - based structures com - carbons atoms) form a single layer having a basal plane prising a fused network of rings ( e . g . , aromatic rings) may 65 comprising a fused network of aromatic rings . Graphene be used in conjunction with the methods and compositions typically includes at least one basal plane containing interior of the present invention . carbon atoms of the fused network , and a perimeter or edge US 9 ,770 ,709 B2 23 24 containing the terminal carbon atoms of the fused network . plurality of carbon fibers may form carbon fiber paper, i . e . , Generally , the side ends or edges of the graphene are a two - dimensional sheet of carbon fibers . The fibers may be saturated with hydrogen atom . However, the graphene mate arranged randomly within the plane of the sheet . rialmay contain non - carbon atoms at its edges , such as OH As used herein , the term “ react" or " reacting ” refers to the and COOH functionalities . It should be noted that the term 5 formation of a bond between two or more components to “ graphene ” includes reference to both single atom layers of produce a stable , isolable compound . For example , a first graphene and multiple layer stacks of graphene . component and a second component may react to form one In some cases , the carbon - based nanostructure is a carbon reaction product comprising the first component and the nanotube. As used herein , the term " carbon nanotube ” is second component joined by a covalent bond . The term given its ordinary meaning in the art and refers to a sub - 10 “ reacting " may also include the use of solvents , catalysts , stantially cylindrical molecule comprising a fused network bases , ligands, or other materials which may serve to pro of six -membered aromatic rings . In some cases , carbon mote the occurrence of the reaction between component( s ) . nanotubes may resemble a sheet of graphite rolled up into a A " stable, isolable compound ” refers to isolated reaction seamless cylindrical structure . It should be understood that products and does not refer to unstable intermediates or the carbon nanotube may also comprise rings other than 15 transition states . A variety of functional groups may be six -membered rings . Typically , at least one end of the carbon installed on the carbon - based nanostructure by varying the nanotube may be capped , i .e ., with a curved or nonplanar alkyne ( e . g . , electrophile ) and nucleophile . aromatic group , although in other embodiments , the carbon As used herein , the term “ reacting ” refers to the formation nanotube need not be capped . Carbon nanotubes may have of a bond between two or more components to produce a a diameter of the order of nanometers and a length on the 20 compound . In some cases, the compound is isolated . In some order of micrometers , resulting in an aspect ratio greater cases , the compound is not isolated and is formed in situ . For than 100 , 1000 , 10 , 000 , or greater . The term " carbon nano - example , a first component and a second component may tube ” includes single - walled nanotubes (SWCNTs ) , multi react to form one reaction product comprising the first walled nanotubes (MWCNTs ) ( e . g ., concentric carbon nano - component and the second component joined by a covalent tubes ) , inorganic derivatives thereof, and the like . In some 25 bond . That is , the term " reacting ” does not refer to the embodiments , the carbon nanotube is a single -walled carbon interaction of solvents , catalysts , bases , ligands, or other nanotube. In some cases , the carbon nanotube is a multi materials which may serve to promote the occurrence of the walled carbon nanotube ( e . g . , a double -walled carbon nano reaction with the component( s ) . tube ) . The term “ substituted ” is contemplated to include all In some cases , the carbon -based nanostructure is a fuller - 30 permissible substituents of organic compounds , " permis ene. As used herein , the term “ fullerene” is given its ordinary sible ” being in the context of the chemical rules of valence meaning in the art and refers to a substantially spherical known to those of ordinary skill in the art . In some cases, molecule generally comprising a fused network of five - " substituted ” may generally refer to replacement of a hydro membered and /or six -membered aromatic rings . For gen with a substituent as described herein . However, “ sub example , C60 is a fullerene which mimics the shape of a 35 stituted , " as used herein , does not encompass replacement soccer ball . The term fullerene may also include molecules and /or alteration of a key functional group by which a having a shape that is related to a spherical shape, such as molecule is identified , e . g ., such that the " substituted ” an ellipsoid . It should be understood that fullerenes may functional group becomes , through substitution , a different comprise rings other than five - or six -membered rings. In functional group . For example, a “ substituted phenyl” must some embodiments , the fullerene may comprise seven - 40 still comprise the phenyl moiety and can not be modified by membered rings, or larger. Fullerenes may include C36 , C50, substitution , in this definition , to become, e . g ., a heteroaryl C60, C70 , C76 , Cg4 , and the like . group such as pyridine . In a broad aspect , the permissible As noted above , carbon -based nanostructures described substituents include acyclic and cyclic , branched and herein may have a high density of charged moieties, i. e ., unbranched , carbocyclic and heterocyclic , aromatic and may have a high ratio of charged moieties to double bonds 45 nonaromatic substituents of organic compounds. Illustrative on the outer surface of the carbon -based nanostructure . substituents include , for example , those described herein . Those of ordinary skill in the art will be able to determine The permissible substituents can be one or more and the the ratio of charged moieties to double bonds on the outer same or different for appropriate organic compounds . For surface of the carbon - based nanostructure . For example , the purposes of this invention , the heteroatoms such as nitrogen number and type of atoms or groups present within a 50 may have hydrogen substituents and / or any permissible carbon -based nanostructure can be determined using differ - substituents of organic compounds described herein which ential scanning calorimetery thermogravimetric analysis , satisfy the valencies of the heteroatoms. This invention is spectrophotometric measurements , elemental analysis , etc . not intended to be limited in any manner by the permissible In one example, a carbon - based nanostructure may be ana substituents of organic compounds . lyzed via elemental analysis in order to calculate the ratio of 55 Examples of substituents include , but are not limited to , charged moieties to double bonds on the outer surface of the alkyl , aryl, aralkyl, cyclic alkyl, heterocycloalkyl, hydroxy, carbon -based nanostructure may be calculated . alkoxy, aryloxy, perhaloalkoxy , aralkoxy , heteroaryl, het In some cases, the carbon -based structure is a carbon eroaryloxy , heteroarylalkyl, heteroaralkoxy , azido , amino , fiber. As used herein , the term “ carbon fiber ” is given its halogen , alkylthio , oxo , acylalkyl, carboxy esters , ordinary meaning in the art and refers to filamentary mate - 60 carboxyl, - carboxamido , nitro , acyloxy , aminoalkyl , alky rials comprising carbon . In some cases, the carbon fiber laminoaryl, alkylaryl, alkylaminoalkyl, alkoxyaryl , ary includes at least about 50 , 60 , 70 , 80 , 90 , or 95 % by weight lamino , aralkylamino , alkylsulfonyl, carboxamidoalkylaryl , carbon . In some cases, the carbon fiber is in the form of carboxamidoaryl, hydroxyalkyl, haloalkyl , alkylaminoalky filamentary tows having a plurality of individual filaments . lcarboxy, aminocarboxamidoalkyl, alkoxyalkyl, perha The diameter of the carbon fibers may be between about 1 65 loalkyl , arylalkyloxyalkyl, and the like . um and about 1 mm , between about 5 um and about 100 um , The term “ aliphatic , ” as used herein , includes both satu between about 5 um and about 10 um . In some cases , a rated and unsaturated , straight chain (i . e ., unbranched ) or US 9 , 770 , 709 B2 25 26 branched aliphatic hydrocarbons, which are optionally sub - includes , but is not limited to , aliphatic , alycyclic , heteroa stituted with one or more functional groups. As will be liphatic , heterocyclic , aryl , heteroaryl , alkylaryl , or alkyl appreciated by one of ordinary skill in the art , “ aliphatic ” is heteroaryl, wherein any of the aliphatic , heteroaliphatic , intended herein to include, but is not limited to , alkyl, alkylaryl, or alkylheteroaryl substituents described above alkenyl, alkynyl moieties . Thus , as used herein , the term 5 and herein may be substituted or unsubstituted , branched or " alkyl ” includes straight and branched alkyl groups . An unbranched , cyclic or acyclic , and wherein any of the aryl or analogous convention applies to other generic terms such as heteroaryl substituents described above and herein may be “ alkenyl, ” “ alkynyl” and the like . Furthermore , as used substituted or unsubstituted . Additional examples of gener herein , the terms " alkyl, " " alkenyl, " " alkynyl” and the like a lly applicable substituents are illustrated by the specific encompass both substituted and unsubstituted groups . In 10 embodiments shown in the Examples that are described certain embodiments , as used herein , “ lower alkyl” is used herein . to indicate those alkyl groups (substituted or unsubstituted , In general , the term “ aryl, " as used herein , refers to a branched or unbranched ) having 1 - 6 carbon atoms. stable mono - or polycyclic , unsaturated moiety having pref In certain embodiments, the alkyl, alkenyl and alkynyl erably 3 - 14 carbon atoms, each of which may be substituted groups employed in the invention contain 1 - 20 aliphatic 15 or unsubstituted . In certain embodiments , the term " aryl” carbon atoms. In certain other embodiments , the alkyl, refers to a planar ring having p - orbitals perpendicular to the alkenyl , and alkynyl groups employed in the invention plane of the ring at each ring atom and satisfying the Huckel contain 1 - 10 aliphatic carbon atoms. In other embodiments , rule where the number of pi electrons in the ring is (4n + 2 ) the alkyl, alkenyl , and alkynyl groups employed in the wherein n is an integer. A mono - or polycyclic , unsaturated invention contain 1 - 8 aliphatic carbon atoms. In still other 20 moiety that does not satisfy one or all of these criteria for embodiments , the alkyl, alkenyl, and alkynyl groups aromaticity is defined herein as “ non - aromatic , ” and is employed in the invention contain 1 -6 aliphatic carbon encompassed by the term " alicyclic . ” atoms. In other embodiments , the alkyl, alkenyl, and alkynyl In general , the term " heteroaryl” , as used herein , refers to groups employed in the invention contain 1 - 4 carbon atoms. a stable mono - or polycyclic , unsaturated moiety having Illustrative aliphatic groups thus include , but are not limited 25 preferably 3 - 14 carbon atoms, each of which may be sub to , for example , methyl, ethyl, n -propyl , isopropyl, allyl, stituted or unsubstituted ; and comprising at least one het n -butyl , sec -butyl , isobutyl, tert -butyl , n - pentyl, sec -pentyl , eroatom selected from O , S , and N within the ring ( i. e ., in isopentyl, tert -pentyl , n -hexyl , sec -hexyl , moieties and the place of a ring carbon atom ). In certain embodiments , the like, which again , may bear one or more substituents. term " heteroaryl” refers to a planar ring comprising at least Alkenyl groups include , but are not limited to , for example , 30 one heteroatom , having p - orbitals perpendicular to the plane ethenyl , propenyl , butenyl, 1 -methyl - 2 - buten - 1 - yl , and the of the ring at each ring atom , and satisfying the Huckel rule like . Representative alkynyl groups include, but are not where the number of pi electrons in the ring is (4n + 2 ) limited to , ethynyl , 2 - propynyl (propargyl ) , 1 - propynyl and wherein n is an integer . the like . It will also be appreciated that aryl and heteroaryl moi The term “ alicyclic ,” as used herein , refers to compounds 35 eties, as defined herein may be attached via an alkyl or which combine the properties of aliphatic and cyclic com - heteroalkylmoiety and thus also include - (alkyl ) aryl , - (het pounds and include but are not limited to cyclic , or poly eroalkyl) aryl , - (heteroalkyl ) heteroaryl, and - (heteroalkyl ) cyclic aliphatic hydrocarbons and bridged cycloalkyl com heteroaryl moieties. Thus, as used herein , the phrases “ aryl pounds , which are optionally substituted with one or more or heteroaryl moieties ” and “ aryl , heteroaryl, - (alkyl ) aryl, functional groups. As will be appreciated by one of ordinary 40 -( heteroalkyl ) aryl, -( heteroalkyl ) heteroaryl , and -( het skill in the art , " alicyclic” is intended herein to include , but eroalkyl) heteroaryl ” are interchangeable . Substituents is not limited to , cycloalkyl, cycloalkenyl, and cycloalkynyl include, but are not limited to , any of the previously men moieties , which are optionally substituted with one ormore tioned substituents , i .e ., the substituents recited for aliphatic functional groups . Illustrative alicyclic groups thus include , moieties, or for other moieties as disclosed herein , resulting but are not limited to , for example , cyclopropyl, CH , - 45 in the formation of a stable compound . cyclopropyl, cyclobutyl, CH - cyclobutyl, cyclopentyl, It will be appreciated that aryl and heteroaryl groups - CH2- cyclopentyl, cyclohexyl, - CH2- cyclohexyl , cyclo - (including bicyclic aryl groups) can be unsubstituted or hexenylethyl, cyclohexanylethyl, norborbyl moieties and the substituted , wherein substitution includes replacement of like , which again , may bear one or more substituents . one or more of the hydrogen atoms thereon independently The term “ heteroalkyl” is given its ordinary meaning in 50 with any one or more of the following moieties including , the art and refers to alkyl groups as described herein in but not limited to : aliphatic ; alicyclic ; heteroaliphatic ; which one or more atoms is a heteroatom ( e . g . , oxygen , heterocyclic ; aromatic ; heteroaromatic ; aryl; heteroaryl ; nitrogen , sulfur, and the like ) . Examples of heteroalkyl alkylaryl; heteroalkylaryl; alkylheteroaryl; heteroalkylhet groups include, but are not limited to , alkoxy, poly (ethylene eroaryl; alkoxy ; aryloxy ; heteroalkoxy ; heteroaryloxy ; alky glycol ), alkyl- substituted amino , tetrahydrofuranyl, piperidi- 55 Ithio ; arylthio ; heteroalkylthio ; heteroarylthio ; F ; Cl; Br; I ; nyl, morpholinyl, etc. OH ; — NO2; CN ; CF3 ; - CH _ F ; CHF2; Some examples of substituents of the above -described CH CF3; CHC12 ; CH2OH ; CH CH2OH ; aliphatic (and other ) moieties of compounds of the invention CH2NH2; CH2SO2CH3; - C ( O ) R ; CO2 (Rx ) ; include, but are not limited to aliphatic ; heteroaliphatic ; aryl; CON (Rx ) 2; - OC (O ) Rx ; - OCO Rx ; - OCON ( R ) 2; heteroaryl; alkylaryl; alkylheteroaryl ; alkoxy ; aryloxy ; het- 60 - N (Rx ) 2 ; - S ( O )RE - S ( O ) 2R ; NR _ (CO ) R , wherein eroalkoxy ; heteroaryloxy ; alkylthio ; arylthio ; heteroalkyl - each occurrence of R , independently includes , but is not thio ; heteroarylthio ; F ; Cl; Br; I ; OH ; — NO2; CN ; limited to , aliphatic , alicyclic , heteroaliphatic , heterocyclic , - CF3 ; CHF2; - CH F ; CH CF3; — CHC12 ; aromatic , heteroaromatic , aryl, heteroaryl, alkylaryl, alkyl - CH2OH ; CH2CH2OH ; CH _ NHz; - CH SO , CH3; heteroaryl, heteroalkylaryl or heteroalkylheteroaryl, - C (O ) Rx CO2( RX ) ; CON (Rx ) 2; OC (O )R , ; 65 wherein any of the aliphatic , alicyclic , heteroaliphatic , het - OCO Rri - OCON (R ) 2 ; — N ( R ) ; - S ( O ) 2R - NR , erocyclic , alkylaryl, or alkylheteroaryl substituents (CO ) R , wherein each occurrence of R independently described above and herein may be substituted or unsubsti US 9 ,770 ,709 B2 27 28 tuted , branched or unbranched , saturated or unsaturated , and unsaturated , and wherein any of the aromatic , heteroaro wherein any of the aromatic , heteroaromatic , aryl, het matic , aryl or heteroaryl substituents described above and eroaryl, -( alkyl ) aryl or -( alkyl ) heteroaryl substituents herein may be substituted or unsubstituted . Additional described above and herein may be substituted or unsubsti - examples of generally applicable substituents are illustrated tuted . Additionally , it will be appreciated , that any two 5 by the specific embodiments described herein . adjacent groups taken together may represent a 4 , 5 , 6 , or The term " heterocycloalkyl” , “ heterocycle ” or “ heterocy 7 -membered substituted or unsubstituted alicyclic or hetero cyclic moiety . Additional examples of generally applicable clic ” , as used herein , refers to compounds which combine substituents are illustrated by the specific embodiments the properties of heteroaliphatic and cyclic compounds and described herein . include , but are not limited to , saturated and unsaturated The term " cycloalkyl ,” as used herein , refers specifically mono - or polycyclic cyclic ring systemshaving 5 - 16 atoms to groups having three to seven , preferably three to ten wherein at least one ring atom is a heteroatom selected from carbon atoms. Suitable cycloalkyls include , but are not O , S and N (wherein the nitrogen and sulfur heteroatoms limited to cyclopropyl, cyclobutyl, cyclopentyl , cyclohexyl, may be optionally be oxidized ), wherein the ring systems are cycloheptyl and the like , which , as in the case of aliphatic , 1515 optionally substituted with one or more functional groups , as alicyclic , heteroaliphatic or heterocyclic moieties , may defined herein . In certain embodiments , the term " hetero optionally be substituted with substituents including, but not cycloalkyl” , “ heterocycle” or “ heterocyclic ” refers to a limited to aliphatic ; alicyclic ; heteroaliphatic ; heterocyclic ; non -aromatic 5 -, 6 - or 7 -membered ring or a polycyclic aromatic ; heteroaromatic ; aryl; heteroaryl ; alkylaryl; het group wherein at least one ring atom is a heteroatom selected eroalkylaryl; alkylheteroaryl; heteroalkylheteroaryl; alkoxy ; 20 from O , S , and N (wherein the nitrogen and sulfur heteroa aryloxy ; heteroalkoxy; heteroaryloxy ; alkylthio ; arylthio ; toms may be optionally be oxidized ) , including , but not heteroalkylthio ; heteroarylthio ; F ; Cl; Br ; 1 ; — OH ; — NO2; limited to , a bi- or tri - cyclic group , comprising fused six - CN ; CFz; CH F ; CHF2; _ CH _ CFz; CHC12 ; membered rings having between one and three heteroatoms - CH2OH ; CH2CH2OH ; CH _ NH2; CH2SO2CH3; independently selected from oxygen , sulfur and nitrogen , - C ( O ) R ; CO ( R ) ; CON ( R ) . ; OC ( O ) R , ; 25 wherein ( i ) each 5 -membered ring has 0 to 2 double bonds , = OCO Rx; - OCON (Rx ) 2 ; — N ( R ) 2 ; S ( O ) Ri - NR each 6 -membered ring has 0 to 2 double bonds and each ( CO )Ry , wherein each occurrence of Rc independently 7 -membered ring has 0 to 3 double bonds, ( ii ) the nitrogen includes, but is not limited to , aliphatic , alicyclic , heteroa and sulfur heteroatoms may be optionally be oxidized , ( iii ) liphatic, heterocyclic, aromatic , heteroaromatic , aryl, het- the nitrogen heteroatom may optionally be quaternized , and eroaryl, alkylaryl, alkylheteroaryl, heteroalkylaryl or het - 30 ( iv ) any of the above heterocyclic rings may be fused to an eroalkylheteroaryl, wherein any of the aliphatic , alicyclic , aryl or heteroaryl ring . Representative heterocycles include , heteroaliphatic , heterocyclic , alkylaryl , or alkylheteroaryl but are not limited to , heterocycles such as furanyl , thio substituents described above and herein may be substituted furanyl, pyranyl, pyrrolyl, thienyl, pyrrolidinyl, pyrazolinyl, or unsubstituted , branched or unbranched , saturated or pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl, unsaturated , and wherein any of the aromatic , heteroaro - 35 piperazinyl, oxazolyl, oxazolidinyl, isooxazolyl, isoxazo matic , aryl or heteroaryl substituents described above and lidinyl, dioxazolyl , thiadiazolyl, oxadiazolyl, tetrazolyl , tri herein may be substituted or unsubstituted . Additional a zolyl, thiatriazolyl , oxatriazolyl, thiadiazolyl, oxadiazolyl, examples of generally applicable substituents are illustrated morpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazo by the specific embodiments shown in the Examples that are lidinyl, dithiazolyl, dithiazolidinyl, tetrahydrofuryl, and ben described herein . 40 zofused derivatives thereof. In certain embodiments , a “ sub The term " heteroaliphatic , " as used herein , refers to stituted heterocycle , or heterocycloalkyl or heterocyclic " aliphatic moieties in which one or more carbon atoms in the group is utilized and as used herein , refers to a heterocycle , main chain have been substituted with a heteroatom . Thus , or heterocycloalkyl or heterocyclic group , as defined above , a heteroaliphatic group refers to an aliphatic chain which substituted by the independent replacement of one , two or contains one or more oxygen , sulfur, nitrogen , phosphorus 45 three of the hydrogen atoms thereon with , but are not limited or silicon atoms, e . g ., in place of carbon atoms. Heteroali to , aliphatic ; alicyclic ; heteroaliphatic ; heterocyclic ; aro phatic moieties may be linear or branched , and saturated or matic ; heteroaromatic ; aryl; heteroaryl; alkylaryl; het unsaturated . In certain embodiments , heteroaliphatic moi- eroalkylaryl; alkylheteroaryl; heteroalkylheteroaryl ; alkoxy ; eties are substituted by independent replacement of one or a ryloxy ; heteroalkoxy ; heteroaryloxy ; alkylthio ; arylthio ; more of the hydrogen atoms thereon with one or more 50 heteroalkylthio ; heteroarylthio ; F ; C1; Br ; I ; - OH ; — NO , ; moieties including, but not limited to aliphatic ; alicyclic ; CN ; CF3; _ CH F ; CHF2; _ CH CFz ; CHC12 ; heteroaliphatic ; heterocyclic ; aromatic ; heteroaromatic ; CH2OH ; CH2CH2OH ; CH NH2; CH2SO2CH3; aryl; heteroaryl; alkylaryl; alkylheteroaryl; alkoxy ; aryloxy ; C ( O ) R ; CO2( RX ); CON (Rx ) 2; OC ( O )Ry ; heteroalkoxy ; heteroaryloxy ; alkylthio ; arylthio ; heteroalky - OCORX ; - OCON (Rx ) 2 ; — N ( R ) 2 ; - S ( O ) Ri - NR Ithio ; heteroarylthio ; F ; Cl; Br ; I ; OH ; — NO2; CN ; 55 (COR , wherein each occurrence of R , independently CF3; CHZF ; CHF2; CH CF3; CHC12 ; includes , but is not limited to , aliphatic , alicyclic , heteroa - CH2OH ; CH2CH2OH ; CH NH2; CH2SO2CH3; liphatic , heterocyclic , aromatic , heteroaromatic , aryl, het - C ( O )Rz ; CO2( RX ) ; CON ( R ) 2 ; OC ( O ) R , ; eroaryl, alkylaryl, alkylheteroaryl, heteroalkylaryl or het - OCO Rx; - OCON (Rx ) 2 ; — N ( R ) 2 ; - S ( O )2R ; - NR eroalkylheteroaryl, wherein any of the aliphatic , alicyclic , ( CO ) R , wherein each occurrence of Rc independently 60 heteroaliphatic , heterocyclic , alkylaryl, or alkylheteroaryl includes , but is not limited to , aliphatic , alicyclic , heteroa substituents described above and herein may be substituted liphatic, heterocyclic , aromatic , heteroaromatic , aryl, het - or unsubstituted , branched or unbranched , saturated or eroaryl, alkylaryl, alkylheteroaryl, heteroalkylaryl or het unsaturated , and wherein any of the aromatic , heteroaro eroalkylheteroaryl, wherein any of the aliphatic , alicyclic , matic , aryl or heteroaryl substituents described above and heteroaliphatic , heterocyclic , alkylaryl, or alkylheteroaryl 65 herein may be substituted or unsubstituted . Additional substituents described above and herein may be substituted examples or generally applicable substituents are illustrated or unsubstituted , branched or unbranched , saturated or by the specific embodiments described herein . US 9 ,770 ,709 B2 29 30 Additionally , it will be appreciated that any of the alicy - ment ). In this example the tertiary alcohols that adorn the clic or heterocyclic moieties described above and herein surface of graphite oxide function as the tertiary allylic may comprise an aryl or heteroaryl moiety fused thereto . alcohols . Direct treatment of these functional groups with a Additional examples of generally applicable substituents are vinyl group equivalent ( e . g . , dimethylacetamide dimethyl illustrated by the specific embodiments described herein . 5 acetal is shown in FIG . 10 ) forms a vinyl allyl alcohol on The terms “ halo ” and “ halogen ” as used herein refer to an GO , in situ . Heating this modified GO then directly breaks atom selected from fluorine, chlorine, bromine , and iodine . the tertiary alcohol bond and allylically forms a new carbon The term “ haloalkyl” denotes an alkyl group , as defined carbon bond while simultaneously forming the new carbonyl above , having one , two , or three halogen atoms attached derivative . In the FIG . 10 , the newly formed carbonyl thereto and is exemplified by such groups as chloromethyl, 10 derivative is an N , N -dimethylamide . bromoethyl, trifluoromethyl, and the like . Functional density determination ( the extent of function The term “ amino , " as used herein , refers to a primary alization , or “ yield ” ) was carried out through the use of ( NH2) , secondary ( NHRX ) , tertiary ( NR _ R , ), or qua X - ray photoelectronic spectroscopy ( XPS ) , thermogravem ternary ( N + R ,RR , ) amine , where Ry , R , and R , are etric analysis ( TGA ) , X -ray diffraction (XRD ) , Raman spec independently an aliphatic, alicyclic , heteroaliphatic , hetero - 15 troscopy, and Fourier transform infrared spectroscopy cyclic , aryl, or heteroaryl moiety , as defined herein . (FTIR ) . Analysis of the rearranged material indicated that Examples of amino groups include, but are not limited to , not only were carbonyl derivatives being successfully incor methylamino , dimethylamino , ethylamino , diethylamino , porated into the graphene surface , but that the remaining, diethylaminocarbonyl, methylethylamino , iso - propylamino , unreacted oxygen functionality was being reduced during piperidino , trimethylamino , and propylamino . 20 the course of the reaction . Therefore, this method simulta The term “ alkyne ” is given its ordinary meaning in the art neously acts as a functionalization process as well as a and refers to branched or unbranched unsaturated hydrocar reduction process . Comparatively , this method reduces the bon groups containing at least one triple bond . Non - limiting graphene oxide to an equivalent degree to the most common examples of alkynes include acetylene, propyne , 1 -butyne , chemical reduction method utilizing hydrazine . 2 -butyne , and the like. The alkyne group may be substituted 25 A variety of other reagents may be used to transform the and / or have one or more hydrogen atoms replaced with a allylic tertiary alcohols on the surface of GO to vinyl allyl functional group , such as a hydroxyl , halogen , alkoxy, alcohols for subsequent Claisen rearrangement. In particu and / or aryl group . lar , triethylorthoformate , trimethylorthoformate, CH2C The term “ alkoxy ” (or “ alkyloxy ' ) , or “ thioalkyl” as used (OCH3 ) 3 and ethylacetoacetate in combination with a weak herein refers to an alkyl group , as previously defined , 30 Bronsted acid source may produce ester groups on the attached to the parent molecular moiety through an oxygen surface of graphene . Additionally, phenyl vinyl sulfoxides atom or through a sulfur atom . In certain embodiments , the and ammonium betaines ( e . g . 3 - ( trimethylammonio )acry alkyl group contains 1 - 20 aliphatic carbon atoms. In certain late ) may produce aldehyde functionality on the surface of other embodiments , the alkyl group contains 1 - 10 aliphatic graphene . Vinyl alcohol groups in the presence of palladium carbon atoms. In other embodiments , the alkyl, alkenyl, and 35 and mercury catalysts can also be used to form the necessary alkynyl groups employed in the invention contain 1 - 8 ali - vinyl allyl alcohol on GO . phatic carbon atoms. In still other embodiments , the alkyl Exemplary Methodology : group contains 1 - 6 aliphatic carbon atoms. In other embodi- 350 mg of graphite oxide and 350 mL of an appropriate ments , the alkyl group contains 1 - 4 aliphatic carbon atoms. dried and degassed solvent ( tetrahydrofuran - THF, dioxane , Examples of alkoxy, include but are not limited to , methoxy, 40 bis ( 2 -methoxyethyl ) ether ) were added to a flame dried and ethoxy , propoxy , isopropoxy, n - butoxy, tert- butoxy , neopen - argon filled flask . The solution was sonicated for 1 hour in toxy and n -hexoxy . Examples of thioalkyl include , but are a bath sonicator to achieve a fine dispersion . The solution not limited to , methylthio , ethylthio , propylthio , isopropyl- was then brought to reflux and the dimethylacetamide dim thio , n -butylthio , and the like. ethylacetal 2 . 4 mL ( 15 . 7 mmol, 2 times molar mass of The term “ alkoxy” refers to the group , O - alkyl. The 45 oxygen content in GO starting material ). The mixture was term “ aryloxy ” refers to the group , O - aryl. The term refluxed for 24h then cooled to room temperature . The " acyloxy ” refers to the group , O -acyl . dispersion was filtered through an anodesic membrane (0 . 2 The term “ independently selected ” is used herein to micron pore diameter ) to obtain a filter cake. The material indicate that the R groups can be identical or different. was then washed with copious amounts of acetone followed These and other aspects described herein will be further 50 by sonication in 20 mL of acetone for 1 h . The slurry was appreciated upon consideration of the following Examples, centrifuged at 14 ,500 rpm to obtain a black sediment. which are intended to illustrate certain particular embodi Sonication in acetone and centrifugation was repeated 3 ments of the invention but are not intended to limit its scope, times with acetone , 2 times with water and again 2 times as defined by the claims. with acetone. The final sediment was dried under vacuum in 55 40 degrees over KOH pellets . EXAMPLE 1 Incorporation of carbonyl functionalized graphene deriva tives as an electronic component into devices allows gra The following example describes the direct conversion of phene derivatives to be used in a variety of applications. One carbon -oxygen bonds on a graphite oxide basal plane to such application would be in replacing graphite as the carbon bound carbonyl groups ( e . g ., see FIG . 10 ) . GO 60 commercial anode material for lithium ion batteries . In this (graphene oxide ) in this example was functionalized using a context many attributes of the functionalized graphene Claisen rearrangement to allylically transpose tertiary alco - derivatives described above (carbonyl binding groups, large hol functional groups found throughout the basal plane of intersheet spacing , nanosheet structure, conductivity ) should graphite oxide into carbon - bound carbonyl derivatives . In allow for high levels of lithium storage / intercalation into the traditional Claisen rearrangements , a vinyl allyl alcohol is 65 nanosheets . Another application is the formation /binding of heated to simultaneously break a carbon -oxygen bond while metallic nanoparticles on the surface of the modified gra forming a carbon - carbon bond ( via a sigmatropic rearrange phene sheets . Not only could a nanoparticle - graphene US 9 ,770 , 709 B2 31 32 derivative composite be produced by mixing the two sub Further work -up of the sample after reaction yields exfo strates , but the carbonyl functionality can also serve to liated material (rGO3b ) with 3 . 7 % nitrogen incorporation " seed ” the formation of nanoparticles. In a similar capacity , which corresponds to one - CH2- C (O ) N (CH3 ) 2 group the graphene derivatives can be used to chemically sense grafted on the surface of GO per 18 C atoms ( 4 - 5 rings ) of individual metal ions by measuring changes in the conduc - 5 the rearranged graphite oxide sheet. Oxygen species content tivity of the graphene sheet upon binding the various metals . may be higher than in rGO3 because of epoxide opening When bound to metal ions the graphene derivative can serve basic conditions introducing more oxygen species onto the surface of rearranged graphene. In some cases , the reaction as a scaffold for catalytic processes. This is relevant for causes simultaneous deoxygenation of graphite oxide at redox - type reactions in which , after the reaction , reduction 10 levels comparable to chemical methods of reduction . Some of the metal ion can occur electrochemically through the degree of deoxygenation can also be noticed in control graphene backbone. Finally , the graphene derivatives can be reactions but it is generally lower ( see Table 1 for C / O ratio ) . utilized to serve as electron transport semiconductors After annealing at 500° C ., the amount of nitrogen was ( n - type materials ) in quantum dot based photovoltaic considerably smaller, for example , due to cleavage of intro devices. duced groups , still accounting for 1 introduced group per 57 graphene carbons that is approximately 20 rings . EXAMPLE 2 By analysis of hi- res XPS data a drop in C / O species The following example described characterization of content was noted in the rearranged material both on the functionalized nanostructures formed using and /or compris basis of C1sd and Ols signals. In the Cis region new ing certain compositions of the present invention . 20 components can be found attributed to amide moieties . The Reaction conditions for this example are substantially nitrogen band is composed of two separate peaks that can be similar as described in Example 1 , except for variations in attributed to amide and most probably charged amide func the solvent and temperature . In addition , control reactions tionalities. were carried out ( e . g . , wherein no DMADMA was added to the reaction mixture ). 25 TABLE 1 In this example , the following abbreviations are employed , and are further described herein : Atomic percentage for the analyzed samples rGoireaction in THF at 60° C ., DMADMA added calculated from XPS data . rGolc - control reaction in THF at 60° C ., no DMADMA Cls OlsOls NisN1s C / 0 * added 30 GO 68. 1 31 . 9 — 2 . 1 rGO2 - reaction in 1 , 4 - dioxane at 100° C . , DMADMA rGO1 84 .6 14 . 1 1 . 33 6 . 2 added rGO2 85 . 5 12 . 4 2 . 1 6 . 3 rGO2c - control reaction in 1 , 4 - dioxane at 100° C . , no G03 85. 8 11. 3 3 . 1 8 .9 DMADMA added rGO3b 79 . 8 16 . 5 5 . 1 rG03 — reaction in diglyme at 150° C ., DMADMA added 20 rGO3b ( 500 ) 85. 7 12 . 9 7. 0 rGolc 74 . 0 26 . 0 4 .0 rGO3c - control reaction in diglyme at 150° C . , no rGO2c 75. 5 24 . 5 3 . 0 DMADMA added ) rGO3c 80 . 1 19 . 9 4 . 0 rGO3b — reaction in diglyme sonicated for 3 h at pH = 9 rGO3c 80 . 1 19 . 9 4 . 0 rGO3b (500 ) — sample annealed in 500° C . for 6h in N atmosphere * C and O atoms of graphene sheets ( without C and O in incorporated functionalities ) Characterization : Throughout the course of the reaction , 40 the reaction mixture turns black shortly after addition of Deoxygenation of the material can be confirmed by TGA DMA ( FIG . 2 ) . The rate of color change is highest for analysis . The TGA mass - loss curve of graphite oxide exhib highest reaction temperature indicating possible deoxygen - its one mass loss region at around 150° C . that is usually ation ofGO . Specifically, FIG . 2 shows the reaction mixture attributed to oxygen species . After rearrangement a gradual (rGO3 ) before (on the left ) and 60 s after (on the right) 45 diminishing of this slope was observed and appearance of addition of DMA . new mass loss region spanning from 230 to 400 ° C . ( see Incorporation of amide functionalities onto the surface of FIG . 4 ) . Specifically , FIG . 4 shows ( top ) TGA and ( bottom ) graphite oxide ( to yield rearranged graphite oxide , rGO ) has dTGA ( rate of mass loss ) of the samples . As has been been investigated by a wide variety of techniques : XPS , demonstrated previously , in this temperature range , one can TGA , FTIR , XRD . XPS is the most commonly used tech - 50 observe loss of ligands bonded by C - C bonds to the nique for quantative as well as qualitative characterization of reduced graphite sheet which may be occurring in this elemental composition of carbon materials . By XPS both material. It is also conspicuous that the second slope is most nitrogen incorporation as well as substantial deoxygenation pronounced for rGO3, which is the sample with highest level of the samples was confirmed . FIG . 2 show the XPS data for of functionalization ( highest nitrogen incorporation as A ) IGO3c and B ) GO3 . Graphite oxide (GO ) and material as shown by XPS ) . from control reactions ( rGolc , rGO2c , rGO3c ) exhibit only In X - ray diffraction experiments , GO exhibits a strong two signals in XPS survey analysis , corresponding to the Cls signal corresponding to the typical graphite oxide spacing of ( around 285 eV ) and Ols (around 532 eV ) peaks. The 8 . 4 Å ( 10 . 50 ) . After rearrangement moderately strong signal carbon to oxygen (C / O ) ratio calculated according to atomic appears at 9 . 3 A (9 .40 ) . Larger spacing than in GO is caused % is 2 . 1 , which is common for graphite oxides obtained by by incorporation of longer substituents ( CH - C ( O ) N Hummer ' s method . All three rearranged graphite oxides 60 (CH ) , ) on the reduced graphite oxide sheets in comparison ( rG01, rGO2, rGO3 ) show an additional band attributed to to native groups ( 0 - , - OH ) . The spacing diminishes the Nis peak ( around 400 eV ) as shown by sample XPS after annealing at 500° C . to 4 . 2 Å which corresponds to spectra in FIG . 2 show . FIG . 3 shows hi- res XPS data of decomposition of introduced groups. Weak and broad sig . ( from top ) Cls , Ols and N1s regions of ( A ) GO and ( B ) nals at 4 . 2 Å for GO and rGO3 can be attributed to small rGO3. Elemental compositions of the samples ( see Table 1 ) 65 domains of poorly exfoliated graphite regions or deoxygen have been calculated . Nitrogen incorporation is higher with ated domains of graphite oxide . FIG . 5 shows XRD spectra increasing reaction temperature . of graphite , GO and rGO3 samples. US 9 ,770 ,709 B2 33 34 FTIR analysis of GO reveals a series of characteristic (OCHZ ) , to create a vinyl- ether intermediate that rearranges signals : 1726 cm - CEO stretching vibrations from carbo to form an allylic ester, which can be further functionalized . nyl and carboxyl groups, 1620 cm - ? C = C stretching, skel - (FIG . 14A ) Examples of further functionalization of the etal vibrations from unoxidized graphitic domains , 1400 allylic ester include saponification (FIG . 14B ) , transamida cm - 1 0 - H bending vibrations, 1300 - 1350 cm C – OH tion (FIG . 14C ) , as well as the synthesis of an alkyne stretching vibrations , 1200 - 1220 cm - 1 breathing vibrations containing group for use in click chemistry (FIG . 14D . from epoxy groups, 1060 cm - l v C - O . For rearranged XRD was used to determine the distance between adja samples a new signal at 1580 cm can be observed that can cent graphene sheets for various substituted graphene mol be attributed to C = C bonds being more pronounced after ecules, as shown in Table 2 below . Substitution on the basal deoxygenation . The strong signal at 1200 cm - for rGO3 plane of the graphene oxide sheets resulted in increased indicates that epoxides are the main oxygen species in this 10 intersheet distance , relative to unsubstituted graphene material in contrast to the starting material (GO ) which is in sheets. agreement with both XPS data as well as reaction mecha Site nism . FIG . 5 shows baseline corrected FTIR spectra of GO , TABLE 2 rGO1 and rG03. GO3b material can be easily dispersed in various organic 15 _ Intersheet distance for various substituted graphene molecules . solvents : NMP, DMF, ACN , and DMSO . Highest stability of dispersions was noted for DMF ( 0 . 1 mg/ mL ) with no Distance between two precipitation observed after 3 weeks. FIG . 7 shows rGO3 adjacent graphene solutions in ( from right ) DMF, NMP and ACN at 0 . 1 mg/ mL Material sheets ( Angstroms ) concentration after 3 weeks of sedimentation . Graphene 3 . 4 20 Graphene Oxide 8 .49 Reduced GO (via NaBH4 ) 5 . 5 - 3 . 4 EXAMPLE 3 ( Adv. Func. Mater. 2009 , 19 , 1987. ) The following examplekample describes thethe synesissynthesis ofOlanlync allylic C laisen -GO (graphene oxide substituted on 9 . 93 amide- functionalized graphene. (FIGS . 11A - B ). As shown basal plane with allylic ethyl esters ) in FIG . 11C , after 1 hour of reacting graphene oxide with 25 Reduced Claisen -GO ( graphene oxide 9 .71 [ ( CH3) 2N ] C (OCH3 ) 2CH3, the solution turns black in color. substitutedesters , upon on being basal treated plane withwith aallylic reducing ethyl Upon completion of the reaction , UV - vis data of the result agent) ing material indicated re - establishment of a conjugated Amide Claisen GO — ( graphene oxide R = H , 10 . 45 A , network , and an FTIR spectrum indicated the presence of substituted on basal plane with allylic | R = Ph , 10. 65 A amide groups by the appearance of amide C = 0 stretching 30 amides ) bands. (FIG . 11D ) XRD data for graphene, graphene oxide , and allylic amide - functionalized graphene oxide is shown in FIG . 11E . XPS plots for graphene oxide , and allylic amide functionalized graphene oxide confirmed the presence of EXAMPLE 7 amide functionality on the graphene surface (dialkylamides 35 7The following example describes the synthesis of func on activated carbon = 399/ 9 eV ) . ( FIGS . 11F - G ) Further tionalized graphene oxides via a Carroll rearrangement. more , TGA data indicated that the functionalization was (FIG . 15B ) All glassware was flame- dried and the reactions covalent in nature and that by increasing the reaction tem were performed under nitrogen atmosphere using standard perature , C - O functionalization decreased and C - C func Schlenk techniques. Graphite powder was received from tionalization increased . 40 Alfa Aeser (natural , 325 -mesh ) and used without further purification . Graphite oxide was synthesized using a modi EXAMPLE 4 fied Hummer ' s method in which NaNO , is excluded . The following example describes saponification ofmodi Acylated Meldrum ' s acid was synthesized according to fied graphene oxide . FIG . 12A shows reaction conditions the following procedure . used for the saponification of an allylic ester- functionalized 45 0 Oxafyl Chloride graphene oxide . The XPS data shown in FIGS . 12B - C cat. DMF indicate that near -complete saponification of the dimethyl R amide group occurred to give a graphene sheet covalently HO DCM functionalized with allylic carboxylates. O C . to r .t . 50 EXAMPLE 5 The following example describes the formation of stable graphene colloids using graphene substituted with allylic V carboxylic acid groups . FIGS . 13A - B show the reversible 55 R 0 conversion of carboxylic acid - functionalized graphene pyr. (2 . 5 eq ) oxide to a potassium salt carboxylate - functionalized gra 2 DCM phene oxide . As shown in FIG . 13C , the chemically con 0 C . to r. t . verted graphene sheets can form stable aqueous colloids through electrostatic stabilization and can remain in solution without the need for polymeric or surfactant stabilizers . FIG . O 13D shows the zeta potential and conductivity data for carboxylic acid - functionalized graphene oxides . O= EXAMPLE 6 65 HO The following example describes the functionalization of 3 graphene oxide via a Johnson Claisen reaction using CH2C US 9 ,770 ,709 B2 35 36 To form compound 2 , 5 .00 g 0 .0218 mol) 3 -( 2 -Bromophe - increased to 130° C . , and the reaction stirred for 21 hr. The nyl) propanoic acid was dissolved in 50 mL dry methylene black dispersion was filtered through a Millipore 0 . 4 um chloride and the resulting solution was stirred and brought to PTFE membrane . The resulting filter cake was washed with 0° C . with an ice- bath and 0. 1 mL DMF added . 2 . 19 mL a copious amount of acetone and then the black material was ( 3 . 19 g . . 0251 mol, 1 . 15 eq ) Freshly distilled oxalyl chloride 5 redispersed in 20 mL CH2Cl2. The dispersion was vortexed was added by syringe over 10 min , and the ice -bath for 10 seconds then centrifuged at 11000 rpm for 10 min and removed . The reaction vessel was sealed and vented through the supernatant discarded . This procedure was repeated 3x with 20 mL CH2Cl2 , followed by 2x20 mL acetone, 3x20 an oil bubbler to monitor the reaction progress . After 4 hrs , mL water, and 2x20 mL acetone . The resulting black slurry or when the reaction was no longer evolving gas , the 10 was then dried in a vacuum oven overnight at 50° C . to solution was degassed with argon for 10 min to promote produce a fine black powder. removal of residual HCI. Alternatively , FIG . 15D shows another method for gen While this reaction was degassing , 3 .61 g Meldrum ' s acid erating an acylketene . Heading 3 -4 hours at 100 C , followed ( . 0251 mol, 1 . 15 eq ) was dissolved in 10 mL dry methylene by 24 hours at 130 C . chloride in a two -necked round bottom flask . The clear 1515 . Typically , two stages of heating were used , as graphite solution was stirred brought to 0° C . with an ice -bath and oxide often loses its oxygen functional groups upon heating 4 .41 mL ( 4 .31 g , 0 .0545 mol, 2 . 5 eq ) dry pyridine was added and reduces back to graphene . To maximize the chances that by syringe over 5 min . To this solution , the solution con the acyl ketene produced will attach to an allylic alcohol, a taining compound 2 was added dropwise by cannula over 30 temperature of 100° C . for 4 hours is maintained to produce min . Upon addition the clear solution became an orange 20 as many B -keto allyl esters on the surface of graphene as dispersion . After addition was complete , the reaction was possible . The second stage of the transformation i. e ., the stirred at 0° C . for 1 hr. Following this , the ice -bath was Carroll rearrangement, is conducted at a relatively higher removed and the reaction stirred at room temperature for an temperature . hour. The now deep red dispersion was poured into a 50 mL FIG . 16 shows thermogravimetric analysis data for vari solution of 2 M HCl containing ice . This mixture was then 25 ous functionalized graphenes compared to unsubstituted poured into a separatory funnel and the organic layer iso - graphene and unsubstituted graphene with physioadsorbed lated . The organic layer was washed with 2x50 mL 2 M HC1 groups . and 1x50 mL brine , dried over MgSO4 and filtered . The FIG . 17 shows X - ray diffraction data for graphene cova deep red solution was adsorbed onto 5 g silica gel and lently functionalized on the basal plane , and FIG . 18 shows purified by column chromatography ( eluent = 9 : 1 hexanes : 30 XPS data for graphene covalently functionalized on the ethyl acetate , with 1 % ACOH added ) to produce 6 .51 g basal plane . Based on this data , the functionalization was ( 0 .0183 mol, 84 % yield ) 5 - ( 3 - ( 2 -bromophenyl ) - 1 -hydroxy - shown to occur many times across the basal plane of the propylidene ) - 2 , 2 -dimethyl - 1 , 3 - dioxane - 4 ,6 - dione (com - graphene sheet, approximately once for every 20 carbon pound 3 ) . rings . The R - groups on the basal plane created a regular The synthesis of a functionalized graphene oxide is 35 lattice with increased D -spacings relative to reduced graph described below . ite and reduced graphite oxide ( 3 . 3 , 3 .45 Å , respectively ) . XPS data also indicated that graphenes with heteroatoms ( e . g ., Br, Cl) include ~ 1 functionalization per 120 carbon atoms of graphene . 40 Additionally , it was found that functionalized graphenes can be used to crease stable dispersions. FIG . 19 shows a + GraphiteGraphite photograph of various samples containing covalently func O= Y tolo + Oxide diglyme tionalized graphene , graphene with physioadsorbed groups , 100° C . for 4 hr and unsubstituted graphene . It was observed that groups then 130° C . for 21 hr 45 attached to graphene via non - covalent, physioadsorption did HOR not impart the same kind of dispersablility as group that are ( 5 mol eq . to oxygen content of graphite oxide ) attached to the basal plane of graphene covalently . While several embodiments described herein have been R? described and illustrated herein , those of ordinary skill in the 50 art will readily envision a variety of other means and /or OH structures for performing the functions and / or obtaining the results and /or one or more of the advantages described herein , and each of such variations and / or modifications is deemed to be within the scope of the present invention . More generally , those skilled in the art will readily appre ciate that all parameters , dimensions, materials , and con figurations described herein are meant to be exemplary and that the actual parameters , dimensions , materials , and / or configurations will depend upon the specific application or 20 mg Graphite oxide was dispersed in 100 mL dry 60 applications for which the teachings described herein is / are diglyme (diethylene glycol dimethyl ether ). The dispersion used . Those skilled in the art will recognize , or be able to was sonicated for 30 min and then 0 .005 mol (5 eq . to ascertain using no more than routine experimentation , many oxygen content of graphite oxide) acylated Meldrum ’ s acid equivalents to the specific embodiments of the invention was added . The dispersion was stirred for 1 hr at room described herein . It is , therefore , to be understood that the temperature then immersed in a 100° C . oil bath . After 65 foregoing embodiments are presented by way of example approximately 10 min the previously brown dispersion only and that, within the scope of the appended claims and turned black . After 4 hours , the oil bath temperature was equivalents thereto , the invention may be practiced other US 9 ,770 ,709 B2 37 38 wise than as specifically described and claimed . The present rying ,” “ having, " " containing, " “ involving ,” “ holding, " and invention is directed to each individual feature, system , the like are to be understood to be open - ended , i . e . , to mean article , material, kit, and / or method described herein . In including but not limited to . Only the transitional phrases addition , any combination of two or more such features , " consisting of” and “ consisting essentially of” shall be systems, articles , materials , kits , and /or methods, if such 5 closed or semi- closed transitional phrases, respectively, as features, systems, articles , materials , kits , and /or methods set forth in the United States Patent Office Manual of Patent are not mutually inconsistent, is included within the scope of Examining Procedures , Section 2111 .03 . the present invention . The indefinite articles “ a ” and “ an , " as used herein in the specification and in the claims , unless clearly indicated to 10 What is claimed : the contrary, should be understood to mean " at least one . ” 1 . A catalyst composition for oxidation of carbon mon The phrase " and/ or , " as used herein in the specification oxide , comprising : and in the claims, should be understood to mean “ either or a graphene or graphene oxide molecule comprising at both " of the elements so conjoined , i .e . , elements that are least one functional group having the structure: conjunctively present in some cases and disjunctively pres - 15 ent in other cases . Other elements may optionally be present other than the elements specifically identified by the “ and / or” clause , whether related or unrelated to those elements be specifically identified unless clearly indicated to the con trary . Thus , as a non - limiting example , a reference to “ A 20 and / or B , " when used in conjunction with open - ended 94 language such as " comprising" can refer, in one embodi ment, to A without B (optionally including elements other wherein : than B ) ; in another embodiment, to B without A (optionally R ' , R ' , and R are the same or different and each is including elements other than A ) ; in another embodiment, to 25 independently a substituent, optionally substituted , both A and B ( optionally including other elements ) ; etc . wherein at least one of R ' , R² , and R3 comprises a As used herein in the specification and in the claims, “ or” . catalytic moiety capable of oxidizing carbon monoxide should be understood to have the same meaning as " and /or ” to carbon dioxide ; and as defined above . For example , when separating items in a G is a carbon atom of the graphene or graphene oxide . list , “ or ” or “ and/ or ” shall be interpreted as being inclusive , 30 2 . A catalyst composition as in claim 1 , wherein the i. e . , the inclusion of at least one , but also including more catalytic moiety comprises a metal. than one , of a number or list of elements , and , optionally, 3 . A catalyst composition as in claim 1 , wherein the additional unlisted items. Only terms clearly indicated to the catalytic moiety comprises Pd , Fe, Ce , Al, Cu , or Ti, or an contrary , such as “ only one of” or “ exactly one of, ” or, when oxide thereof. used in the claims, “ consisting of, ” will refer to the inclusion 35 4 . A catalyst composition as in claim 1 , wherein the of exactly one element of a number or list of elements . In catalytic moiety comprises Pd nanoclusters , Fe2O3, FeOOH , general , the term “ or ” as used herein shall only be inter or TiOOH . preted as indicating exclusive alternatives ( i. e . " one or the 5 . A catalyst composition as in claim 2 , wherein at least other but not both ” ) when preceded by terms of exclusivity , one of R1, R2 , and R3 is capable of binding a metal . such as “ either, " " one of, " " only one of, ” or “ exactly one of. ” 40 6 . A catalyst composition as in claim 5 , wherein at least " Consisting essentially of, ” when used in the claims, shall one of R ' , R ? , and R8 comprises nitrogen , sulfur, or phos have its ordinary meaning as used in the field of patent law . phorus . As used herein in the specification and in the claims, the 7 . A catalyst composition as in claim 5 , wherein at least phrase " at least one, ” in reference to a list of one or more one of R ' , R², and R3 comprises a positively or a negatively elements, should be understood to mean at least one element 45 charged group . selected from any one or more of the elements in the list of 8 . A catalyst composition as in claim 1 , wherein the elements , but not necessarily including at least one of each catalytic moiety is capable of reducing oxygen . and every element specifically listed within the list of 9 . A catalyst composition as in claim 1 , wherein the elements and not excluding any combinations of elements in catalytic moiety is capable of reducing nitric oxide . the list of elements. This definition also allows that elements 50 10 . A catalyst composition as in claim 1 , wherein : may optionally be present other than the elements specifi - R * is hydrogen , alkyl, aryl, alkenyl, cycloalkyl, het cally identified within the list of elements to which the eroalkyl, heteroaryl , N (R4 ) 2 , SR4, Si( R4 ) 2 , OR , or phrase “ at least one ” refers , whether related or unrelated to OM , any of which is optionally substituted , those elements specifically identified . Thus, as a non - limit M is a metal or cationic species; and ucu , ing example , “ at least one of A and B ” (or , equivalently , “ at 55 each R * is independently a substituent, optionally substi least one of Aor B , " or, equivalently “ at least one of A and / or tuted . B ” ) can refer , in one embodiment, to at least one , optionally 11 . A catalyst composition as in claim 10 , wherein : including more than one , A , with no B present ( and option R is aryl, heteroalkyl, heteroaryl, N (R4 ) 2, SR “ , Si( R + ) 2, ally including elements other than B ) ; in another embodi OR , or OM , any of which is optionally substituted , ment, to at least one , optionally including more than one , B , 60 M is a metal ; and with no A present and optionally including elements other each R4 is independently a substituent, optionally substi than A ); in yet another embodiment, to at least one, option tuted . ally including more than one , 12. A catalyst composition as in claim 11, wherein each R4 A , and at least one, optionally including more than one , B is independently hydrogen , an organic substituent, or a ( and optionally including other elements ) ; etc . 65 metal- containing substituent, optionally substituted . In the claims, as well as in the specification above , all 13 . A catalyst composition as in claim 10 , wherein R3 is transitional phrases such as comprising, ” “ including, " " car- OR4 or N (R4 ) 2 . US 9 ,770 ,709 B2 39 40 14 . A catalyst composition as in claim 10 , wherein each R4 is the same or different and each is independently hydrogen , alkyl, cycloalkyl, haloalkyl, heteroalkyl, aryl, heteroaryl, or OH , any of which is optionally substituted . 15 . A catalyst composition as in claim 10 , wherein R3 is 5 N (CH3 ) 2 , NH - phenyl, NH - biphenyl , NHCH ( C = CH ) , OH , OMe, OET, OM , where M is a metal ion , OCH , ( C = CH ) , OCH CH2( 2 -bromophenyl ) , OCH (adamantyl ) , or OCH _ C (4 -chlorophenyl ) z. 16 . A catalyst composition as in claim 10 , wherein R4 is 10 alkyl substituted with an unsubstituted or substituted aryl or an unsubstituted or substituted cycloalkyl. 17 . A catalyst composition as in claim 10 , wherein : R and R2 are the same or different and each is indepen dently hydrogen , alkyl, heteroalkyl , cycloalkyl, alk - 15 enyl, or aryl, any of which is optionally substituted . 18 . A catalyst composition as in claim 17, wherein Rand R2 are both hydrogen . * * * *